WO2016152466A1 - Molded article for medical use, extrusion molding method for molded article for medical use, and extrusion molding device for molded article for medical use - Google Patents
Molded article for medical use, extrusion molding method for molded article for medical use, and extrusion molding device for molded article for medical use Download PDFInfo
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- WO2016152466A1 WO2016152466A1 PCT/JP2016/056880 JP2016056880W WO2016152466A1 WO 2016152466 A1 WO2016152466 A1 WO 2016152466A1 JP 2016056880 W JP2016056880 W JP 2016056880W WO 2016152466 A1 WO2016152466 A1 WO 2016152466A1
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- WIPO (PCT)
- Prior art keywords
- composition
- extruder
- molded article
- medical
- mass
- Prior art date
Links
- 238000001125 extrusion Methods 0.000 title claims abstract description 34
- 238000000034 method Methods 0.000 title claims description 25
- 239000000203 mixture Substances 0.000 claims abstract description 86
- 239000000344 soap Substances 0.000 claims abstract description 53
- 229920000915 polyvinyl chloride Polymers 0.000 claims abstract description 43
- 239000004800 polyvinyl chloride Substances 0.000 claims abstract description 43
- 239000004014 plasticizer Substances 0.000 claims abstract description 34
- 239000011701 zinc Substances 0.000 claims abstract description 28
- 229920005989 resin Polymers 0.000 claims abstract description 27
- 239000011347 resin Substances 0.000 claims abstract description 27
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 24
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 23
- 239000011575 calcium Substances 0.000 claims abstract description 23
- 239000004593 Epoxy Substances 0.000 claims abstract description 18
- 150000002148 esters Chemical class 0.000 claims abstract description 16
- 230000020169 heat generation Effects 0.000 claims abstract description 16
- 239000007787 solid Substances 0.000 claims abstract description 12
- 239000008247 solid mixture Substances 0.000 claims abstract description 8
- 238000010008 shearing Methods 0.000 claims description 16
- 239000008280 blood Substances 0.000 claims description 6
- 210000004369 blood Anatomy 0.000 claims description 6
- 238000000465 moulding Methods 0.000 claims description 6
- 238000002844 melting Methods 0.000 claims description 2
- 230000008018 melting Effects 0.000 claims description 2
- 238000001802 infusion Methods 0.000 claims 2
- 238000005516 engineering process Methods 0.000 abstract 1
- 230000001105 regulatory effect Effects 0.000 abstract 1
- 239000000047 product Substances 0.000 description 54
- 239000008188 pellet Substances 0.000 description 20
- 239000011342 resin composition Substances 0.000 description 19
- 239000003381 stabilizer Substances 0.000 description 14
- 238000004040 coloring Methods 0.000 description 12
- 230000001954 sterilising effect Effects 0.000 description 12
- 238000004659 sterilization and disinfection Methods 0.000 description 12
- 238000013329 compounding Methods 0.000 description 10
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- -1 3-mercaptopropionic acid ester Chemical class 0.000 description 6
- 238000002845 discoloration Methods 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 5
- 230000002093 peripheral effect Effects 0.000 description 5
- 239000012321 sodium triacetoxyborohydride Substances 0.000 description 5
- 239000006057 Non-nutritive feed additive Substances 0.000 description 4
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 4
- 239000008116 calcium stearate Substances 0.000 description 4
- 235000013539 calcium stearate Nutrition 0.000 description 4
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 4
- 238000001308 synthesis method Methods 0.000 description 4
- 238000012546 transfer Methods 0.000 description 4
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 4
- 239000004803 Di-2ethylhexylphthalate Substances 0.000 description 3
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000010894 electron beam technology Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000049 pigment Substances 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 230000005855 radiation Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 3
- 239000004808 2-ethylhexylester Substances 0.000 description 2
- ZVFDTKUVRCTHQE-UHFFFAOYSA-N Diisodecyl phthalate Chemical compound CC(C)CCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC(C)C ZVFDTKUVRCTHQE-UHFFFAOYSA-N 0.000 description 2
- KRADHMIOFJQKEZ-UHFFFAOYSA-N Tri-2-ethylhexyl trimellitate Chemical compound CCCCC(CC)COC(=O)C1=CC=C(C(=O)OCC(CC)CCCC)C(C(=O)OCC(CC)CCCC)=C1 KRADHMIOFJQKEZ-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- HBGGXOJOCNVPFY-UHFFFAOYSA-N diisononyl phthalate Chemical compound CC(C)CCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCC(C)C HBGGXOJOCNVPFY-UHFFFAOYSA-N 0.000 description 2
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000003978 infusion fluid Substances 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000012567 medical material Substances 0.000 description 2
- 229940127554 medical product Drugs 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 238000005649 metathesis reaction Methods 0.000 description 2
- 235000015097 nutrients Nutrition 0.000 description 2
- 125000001117 oleyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])/C([H])=C([H])\C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229920002545 silicone oil Polymers 0.000 description 2
- 239000003549 soybean oil Substances 0.000 description 2
- 235000012424 soybean oil Nutrition 0.000 description 2
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- GPZYYYGYCRFPBU-UHFFFAOYSA-N 6-Hydroxyflavone Chemical compound C=1C(=O)C2=CC(O)=CC=C2OC=1C1=CC=CC=C1 GPZYYYGYCRFPBU-UHFFFAOYSA-N 0.000 description 1
- QZCLKYGREBVARF-UHFFFAOYSA-N Acetyl tributyl citrate Chemical compound CCCCOC(=O)CC(C(=O)OCCCC)(OC(C)=O)CC(=O)OCCCC QZCLKYGREBVARF-UHFFFAOYSA-N 0.000 description 1
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 206010037660 Pyrexia Diseases 0.000 description 1
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 description 1
- 150000001278 adipic acid derivatives Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- VBICKXHEKHSIBG-UHFFFAOYSA-N beta-monoglyceryl stearate Natural products CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- ZFMQKOWCDKKBIF-UHFFFAOYSA-N bis(3,5-difluorophenyl)phosphane Chemical compound FC1=CC(F)=CC(PC=2C=C(F)C=C(F)C=2)=C1 ZFMQKOWCDKKBIF-UHFFFAOYSA-N 0.000 description 1
- 230000000740 bleeding effect Effects 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- HIAAVKYLDRCDFQ-UHFFFAOYSA-L calcium;dodecanoate Chemical compound [Ca+2].CCCCCCCCCCCC([O-])=O.CCCCCCCCCCCC([O-])=O HIAAVKYLDRCDFQ-UHFFFAOYSA-L 0.000 description 1
- HRBZRZSCMANEHQ-UHFFFAOYSA-L calcium;hexadecanoate Chemical compound [Ca+2].CCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCC([O-])=O HRBZRZSCMANEHQ-UHFFFAOYSA-L 0.000 description 1
- ZCZLQYAECBEUBH-UHFFFAOYSA-L calcium;octadec-9-enoate Chemical compound [Ca+2].CCCCCCCCC=CCCCCCCCC([O-])=O.CCCCCCCCC=CCCCCCCCC([O-])=O ZCZLQYAECBEUBH-UHFFFAOYSA-L 0.000 description 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical class OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 230000003013 cytotoxicity Effects 0.000 description 1
- 231100000135 cytotoxicity Toxicity 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 229960001545 hydrotalcite Drugs 0.000 description 1
- 229910001701 hydrotalcite Inorganic materials 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000000944 linseed oil Substances 0.000 description 1
- 235000021388 linseed oil Nutrition 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 239000012778 molding material Substances 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-N o-dicarboxybenzene Natural products OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical class OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 150000003021 phthalic acid derivatives Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 238000010094 polymer processing Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 238000010558 suspension polymerization method Methods 0.000 description 1
- TUUQISRYLMFKOG-UHFFFAOYSA-N trihexyl 2-acetyloxypropane-1,2,3-tricarboxylate Chemical compound CCCCCCOC(=O)CC(C(=O)OCCCCCC)(OC(C)=O)CC(=O)OCCCCCC TUUQISRYLMFKOG-UHFFFAOYSA-N 0.000 description 1
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 229940098697 zinc laurate Drugs 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 229940012185 zinc palmitate Drugs 0.000 description 1
- 229940057977 zinc stearate Drugs 0.000 description 1
- LPEBYPDZMWMCLZ-CVBJKYQLSA-L zinc;(z)-octadec-9-enoate Chemical compound [Zn+2].CCCCCCCC\C=C/CCCCCCCC([O-])=O.CCCCCCCC\C=C/CCCCCCCC([O-])=O LPEBYPDZMWMCLZ-CVBJKYQLSA-L 0.000 description 1
- GPYYEEJOMCKTPR-UHFFFAOYSA-L zinc;dodecanoate Chemical compound [Zn+2].CCCCCCCCCCCC([O-])=O.CCCCCCCCCCCC([O-])=O GPYYEEJOMCKTPR-UHFFFAOYSA-L 0.000 description 1
- GJAPSKMAVXDBIU-UHFFFAOYSA-L zinc;hexadecanoate Chemical compound [Zn+2].CCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCC([O-])=O GJAPSKMAVXDBIU-UHFFFAOYSA-L 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08L27/06—Homopolymers or copolymers of vinyl chloride
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/92—Measuring, controlling or regulating
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/15—Heterocyclic compounds having oxygen in the ring
- C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
- C08K5/1515—Three-membered rings
Definitions
- the present invention relates to a medical molded article, a method for extruding a medical molded article, and an apparatus for extruding a medical molded article.
- soft polyvinyl chloride resin has been widely used as a medical material.
- Medical devices are used in the vicinity of patients whose contacted blood is returned to the living body, inserted into living tissue, or who are weak, so the safety is considerably considered.
- it is used in a sterilized form, and radiation sterilization, ethylene oxide sterilization, or high-pressure steam sterilization is generally adopted as the sterilization method.
- radiation sterilization is hygienic and has little damage to medical materials because there is no concern about residual ethylene oxide gas like ethylene oxide sterilization, and medical instruments are not exposed to high temperatures like high-pressure steam sterilization. It has been adopted as a sterilization method.
- the soft polyvinyl chloride resin or a compounding agent thereof deteriorates / denaturates due to radiation or heating, causing problems such as promotion of coloring.
- Patent Document 1 reports a molded product that hardly discolors even during electron beam sterilization.
- Patent Document 1 is characterized in that it is molded from a polyvinyl chloride resin composition containing a specific amount of a 3-mercaptopropionic acid ester of a trihydric or higher polyhydric alcohol.
- the molded article described in Patent Document 1 is certainly a molded article that is excellent in resistance to discoloration against electron beam sterilization and hardly discolors after electron beam sterilization.
- a medical molded product made of polyvinyl chloride resin is a general-purpose product and is desired to be manufactured at a lower cost than other high-performance medical devices. For this reason, in consideration of cost reduction, it is desired to reduce the type and amount of the compounding agent (additive) as much as possible.
- an object of the present invention is to provide a technique capable of inexpensively manufacturing a medical molded product with reduced coloring (discoloration).
- the present inventor has found that the degree of coloration is low (high whiteness and low yellowness) even when the amount of metal soap that is a heat stabilizer is reduced.
- the inventors have found a technique for producing a vinyl resin medical molded article and have completed the present invention.
- a molded product for medical use which is formed by extrusion molding a composition containing a part (total amount) and has a whiteness (WI) of 25 or more and a yellowness (YI) of 3.5 or less. Achieved.
- a method for extruding a medical molded article that achieves the above-described object is to extrude the above-described composition and have a whiteness (WI) of 25 or more and a yellowness (YI) of 3.5 or less.
- WI whiteness
- YI yellowness
- the composition formed in a solid state on the screw of an extruder formed with the same groove depth is adjusted to a supply amount adjusted so as not to generate shear heat generation in the composition in the extruder. And supply.
- the solid composition supplied to the screw is melted by applying heat from a heater.
- the said composition of the molten state extruded from the said extruder is shape
- An apparatus for extruding a medical molded article that achieves the above-described object extrudes the above-described composition and has a whiteness (WI) of 25 or more and a yellowness (YI) of 3.5 or less.
- the extrusion molding apparatus includes an extruder in which a screw formed with the same groove depth is rotatably disposed in a barrel, and supplies the composition formed in a solid state to the screw and the composition.
- a feeder capable of adjusting the supply amount of the metal, a heater for applying heat to melt the solid composition supplied to the screw, and the molten composition extruded from the extruder, And a die that is formed into a shape. And the said feeder adjusts the supply amount of the said composition to the quantity which does not produce a shearing heat_generation
- the medical molded article of the present invention has a low degree of coloring (high whiteness and low yellowness) even with a small amount of metal soap. Therefore, the medical molded article of the present invention can be manufactured at low cost.
- a screw formed with the same groove depth is used, and a composition formed into a solid state is subjected to shear heat generation in the composition in an extruder.
- Supply is made with a supply amount adjusted to an amount that does not occur. For this reason, it is suppressed that a composition stagnates in an extruder, and also it is suppressed that a composition heat-extracts excessively in an extruder.
- As a result of suppressing two factors that cause burns in molded products even with a small amount of metal soap, it is possible to produce medical molded products with low coloring (high whiteness and low yellowness) at low cost. .
- FIG. 1 It is a schematic block diagram which shows the extrusion molding apparatus of the medical molded product which concerns on embodiment of this invention. It is sectional drawing which shows the principal part of the extrusion molding apparatus of the medical molded product shown in FIG.
- the first of the present invention is based on 100 parts by mass of polyvinyl chloride resin, 30 to 160 parts by mass of ester plasticizer, 5 to 25 parts by mass of epoxy plasticizer, and 0.01 to 0.1 mass of zinc soap and calcium soap.
- a medical molded article obtained by extrusion molding of a composition containing parts (total amount) and having a whiteness (WI) of 25 or more and a yellowness (YI) of 3.5 or less. provide.
- a medical molded article satisfying the above configuration has a low degree of coloring (high whiteness and low yellowness) even with a small amount of metal soap. Therefore, the medical molded article of the present invention can be manufactured at low cost.
- general-purpose medical polyvinyl chloride resin molded products are used for various applications such as infusion solutions, transfusion bags, and connecting tubes.
- the molded product preferably has a low yellowness and a high whiteness so that the state of the molded product content (eg, blood, nutrients, etc.) (eg, liquid flow, color) can be easily observed. It is.
- the state of the molded product content eg, blood, nutrients, etc.
- attempts have been made to suppress discoloration and coloring using various additives.
- such general-purpose medical molded articles are used in large quantities for various purposes, and therefore are required to be inexpensive.
- the medical molded article of the present invention is produced by a specific means as described in detail below, so that even if a small amount of stabilizer (zinc soap and calcium soap) is used, the whiteness degree Therefore, it is possible to produce a medical molded product having a high yellowness and a low yellowness.
- stabilizer Zinc soap and calcium soap
- X to Y indicating a range includes X and Y, and means “X or more and Y or less”. Unless otherwise specified, measurement of operation and physical properties is performed under conditions of room temperature (20 to 25 ° C.) / Relative humidity 40 to 50%.
- the medical molded article of the present invention is produced by extruding a specific composition (polyvinyl chloride resin composition) as described above.
- the medical molded article of the present invention has a whiteness (WI) of 25 or more and a yellowness (YI) of 3.5 or less.
- WI whiteness
- YI yellowness
- a molded product having a high whiteness and a low coloration degree (yellowness) exhibits high visibility. Therefore, a liquid (for example, blood, nutrients, etc.) is poured into the molded product (for example, a tube).
- the state for example, the flow of a liquid, a color
- the whiteness of the medical molded product is preferably 26 or more, more preferably 27 or more, and particularly preferably 28 or more.
- an upper limit in particular is not set, but about 50 or less is enough.
- the yellowness of the medical molded article is preferably 3 or less, more preferably 2 or less, and particularly preferably 1.5 or less.
- the yellow degree of a medical molded product is so preferable that it is low, a minimum in particular is not set but it is 0 or more.
- the whiteness and yellowness of a medical molded product are values measured according to the following method.
- sample tube having an inner diameter of 3.0 mm and an outer diameter of 4.4 mm is extruded (sample tube).
- the polyvinyl chloride resin is not particularly limited, and a polyvinyl chloride resin usually used for medical purposes is used in the same manner. For this reason, as the polyvinyl chloride resin, a synthetic product or a commercially available product may be used. Preferably, a polyvinyl chloride resin having a degree of polymerization of about 1000 to 2000 is used.
- a polyvinyl chloride resin having a degree of polymerization of about 1000 to 2000 is used as examples of commercially available products.
- polyvinyl chloride resins S-400, S1006, S1007, S1008, S1001, S1001N, S1003, S1003N, S1004, KS-1700, KS-2500, KS-3000 or more, Manufactured by Kaneka Corporation.
- the method for synthesizing the polyvinyl chloride resin is not particularly limited, and examples thereof include a suspension polymerization method.
- the said polyvinyl chloride resin may be used independently and may be used in combination of
- an ester plasticizer is blended in an amount of 30 to 160 parts by mass, preferably 40 to 100 parts by mass with respect to 100 parts by mass of the polyvinyl chloride resin.
- the ester plasticizer becomes difficult to be uniformly mixed, and thus it may be difficult to manufacture as a compound of the polyvinyl chloride resin composition.
- the amount of the ester plasticizer is less than 30 parts by mass, the compatibility with the polyvinyl chloride resin is lowered, and the desired flexibility cannot be obtained, which is not preferable.
- ester plasticizers include, but are not limited to, for example, trimellitic esters such as tri-2-ethylhexyl trimellitic acid (TOTM); tributyl acetyl citrate, trihexyl acetyl citrate, trihexyl n-butyryl citrate, etc.
- trimellitic esters such as tri-2-ethylhexyl trimellitic acid (TOTM); tributyl acetyl citrate, trihexyl acetyl citrate, trihexyl n-butyryl citrate, etc.
- Citric acid esters such as bis (2-ethylhexyl) phthalate (DEHP) (dioctyl phthalate (DOP)), diisononyl phthalate (DINP), diisodecyl phthalate (DIDP), dibutyl phthalate (DBP);
- Examples include adipic acid esters such as dioctyl adipate and diisononyl adipate; and phosphate esters such as tricresyl phosphate.
- trimellitic acid ester and phthalic acid ester are preferable, and TOTM and DEHP are more preferable from the viewpoints of flexibility (particularly low temperature flexibility), thermal stability, and safety.
- ester plasticizer used in the present invention a synthetic product or a commercially available product may be used.
- examples of commercially available products include TOTM-NB manufactured by Jay Plus.
- Examples of the synthesis method include a method of esterifying by mixing trimellitic anhydride and alcohol.
- ester plasticizers may be used alone or in combination of two or more.
- Epoxy plasticizer In the polyvinyl chloride resin composition according to the present invention, an epoxy plasticizer is blended in an amount of 5 to 25 parts by mass, preferably 7 to 15 parts by mass with respect to 100 parts by mass of the polyvinyl chloride resin.
- Epoxy plasticizers act as plasticizers and processing aids.
- the epoxy plasticizer also acts as a heat stabilization aid for zinc soap and calcium soap (stabilizer).
- stabilizer zinc soap and calcium soap
- epoxy plasticizer examples include epoxies such as epoxidized soybean oil and epoxidized linseed oil.
- the epoxy plasticizer used in the present invention may be a synthetic product or a commercially available product.
- Examples of commercially available products include O-130P and O-180A manufactured by ADEKA Corporation.
- Examples of the synthesis method include a method of directly epoxidizing an alkene.
- the above epoxy plasticizers may be used alone or in combination of two or more.
- zinc soap and calcium soap are used as a stabilizer with respect to 100 parts by mass of the polyvinyl chloride resin as a total of 0.01 to 0.1 parts by mass, The amount is preferably 0.03 to 0.08 parts by mass.
- the transparency of a polyvinyl chloride resin composition will fall.
- the coloration of the polyvinyl chloride resin after sterilization tends to increase.
- the blending amount is too small, heat resistance and discoloration resistance may be lowered, or coloring may be induced.
- the zinc soap is not particularly limited, but those containing lauryl group, palmityl group, stearyl group or oleyl group such as zinc laurate, zinc palmitate, zinc stearate and zinc oleate are preferably used. Those having such an alkyl group are suitable for medical use from the viewpoint of safety.
- the zinc soap used in the present invention may be a synthetic product or a commercial product.
- a commercial item the zinc stearate by Sakai Chemical Industry Co., Ltd. is mentioned, for example.
- Examples of the synthesis method for synthesizing zinc soap include a method in which an aqueous solution of an alkali metal salt of a fatty acid and an inorganic metal salt are subjected to a metathesis reaction.
- the calcium soap is not particularly limited, but, like the zinc soap, contains a lauryl group such as calcium laurate, calcium palmitate, calcium stearate, or calcium oleate, a palmityl group, a stearyl group, or an oleyl group. Is preferably used. Those having such an alkyl group are particularly suitable for medical use from the viewpoint of safety.
- the calcium soap used in the present invention may be a synthetic product or a commercially available product.
- Examples of commercially available products include calcium stearate manufactured by Sakai Chemical Industry Co., Ltd.
- a synthesis method for synthesizing calcium soap for example, a method of metathesis reaction between an aqueous solution of an alkali metal salt of a fatty acid and an inorganic metal salt can be mentioned.
- the zinc soap and calcium soap may be used alone or in combination of two or more.
- the polyvinyl chloride resin composition according to the present invention contains zinc soap and calcium soap.
- the mixing ratio of zinc soap and calcium soap is not particularly limited, but preferably the mixing ratio of zinc soap and calcium soap (mass ratio of zinc soap: calcium soap) is preferably 1: 1 to 3, more preferably. Is 1: 1-2. With such a mixing ratio, coloring can be significantly reduced, and a molded product for medical use having higher whiteness and lower yellowness can be produced at a lower cost.
- Zinc soap and calcium soap may be blended separately in the polyvinyl chloride resin composition, but a mixture blended in advance at a predetermined ratio may be blended. In the latter case, a commercially available product may be used as the mixture. Examples of commercially available products include, for example, stabilizers ADEKA STAB series SC-12, 593, 37, SC-308E (manufactured by ADEKA Corporation).
- the polyvinyl chloride resin composition forming the molded article of the present invention can achieve the object of the present invention, and can further contain other optional components as long as the original characteristics are not particularly impaired.
- these optional components include metal oxides, heat resistance improvers, lubricants, pigments, surfactants, and processing aids.
- the metal oxide is not particularly limited, and examples thereof include magnesium oxide, calcium oxide, and zinc oxide.
- the heat resistance improver is not particularly limited, and examples thereof include pentaerythritols and hydrotalcite.
- the lubricant is not particularly limited, and examples thereof include silicone oil.
- the pigment is not particularly limited, and examples thereof include metal complex pigments.
- the surfactant is not particularly limited, and examples thereof include stearic acid monoglyceride.
- the processing aid is not particularly limited, and examples thereof include acrylic polymer processing aids.
- the compounding amounts of these compounding agents are not particularly limited as long as they do not impair the safety, heat resistance, and coloring resistance of the polyvinyl chloride resin composition.
- the total amount of these compounding agents is preferably 0.1 to 0.5 parts by mass with respect to 100 parts by mass of the polyvinyl chloride resin composition according to the present invention.
- the polyvinyl chloride resin composition according to the present invention is not particularly limited, and is produced by extruding the polyvinyl chloride resin composition.
- FIG. 1 is a schematic configuration diagram illustrating an extrusion molding apparatus 10 for a medical molded product according to an embodiment of the present invention
- FIG. 2 is a cross-sectional view illustrating a main part of the extrusion molding apparatus 10 for a medical molded product illustrated in FIG. It is.
- the extrusion molding apparatus 10 of the present embodiment can be summarized as follows.
- the composition 11 described above is extruded, and the whiteness (WI) is 25 or more and the yellowness (Y ..I.),
- WI whiteness
- Y ..I. yellowness
- the extrusion molding apparatus 10 includes an extruder 20 in which a screw 21 in which the depth d of the groove 22 is formed to the same depth is rotatably disposed in a barrel 23, and a composition 11 formed in a solid form in the screw 21.
- Feeder 30 capable of supplying and adjusting the supply amount of composition 11, heaters 41, 42, 43 for applying heat to melt solid composition 11 supplied to screw 21, and extruded from extruder 20 And a die 50 for molding the molten composition 11 into the shape of the medical molded article 12. Then, the feeder 30 adjusts the supply amount of the composition 11 to an amount that does not cause the composition 11 to generate shear heat in the extruder 20.
- the composition 11 formed in a solid form is applied to the screw 21 of the extruder 20 in which the depth d of the groove 22 is formed to the same depth.
- the composition 11 is supplied at a supply amount adjusted so as not to cause shearing heat generation.
- the solid composition 11 supplied to the screw 21 is melted by applying heat from the heaters 41, 42, 43, and the molten composition 11 extruded from the extruder 20 is molded by the die 50 for medical use.
- the shape of the product 12 is formed. Details will be described below.
- the composition 11 has an ester plasticizer of 30 to 160 parts by mass, an epoxy plasticizer of 5 to 25 parts by mass, and zinc soap and calcium soap of 0.01 to 0.00 per 100 parts by mass of the polyvinyl chloride resin. 1 part by mass (total amount) is included.
- the composition 11 is formed into a solid pellet.
- the pellet 11 (composition) is heat-dried in a dehumidifying dryer (not shown).
- the pellet 11 is kept at the moisture content specified by the resin manufacturer under the drying conditions recommended by the resin manufacturer.
- the pellet 11 has a spherical shape with a diameter of 3 to 4 mm, for example.
- the shape of the pellet 11 is not limited to a spherical shape, and may have a short bar shape, for example.
- the extruder 20 has a barrel 23 also called a cylinder, a screw 21 that is rotatably held in the barrel 23, and a gear train 24 and a motor 25 that rotationally drive the screw 21.
- the barrel 23 is opened with an inlet for feeding a molding material.
- a feed zone C1, a transfer zone C2, and a metering zone C3 are formed in order from the proximal end side to the distal end side.
- the supply section 26 is configured by the feed zone C1 of the screw 21 and the portion where the base end of the screw 21 faces the charging port of the barrel 23.
- the extruder 20 is preferably a single-screw extruder.
- the screw 21 has a main body part 21a and a flight part 21b protruding from the outer peripheral surface of the main body part 21a.
- the flight part 21b extends spirally on the outer peripheral surface of the main body part 21a.
- the main body 21a has a straight pipe shape with a constant outer diameter.
- the flight part 21b has a constant outer diameter. Therefore, the screw 21 is formed so that the depth d of the groove 22 is the same.
- the gap dimension between the feed zone C1 of the screw 21 and the inner peripheral surface of the barrel 23, the gap dimension between the transfer zone C2 and the inner peripheral surface of the barrel 23, and between the metering zone C3 and the inner peripheral surface of the barrel 23 The gap dimensions are all the same.
- the feeder 30 includes a preliminary hopper 31 to which the pellets 11 are supplied by a loader (not shown), a main hopper 32 connected to the inlet of the barrel 23 of the extruder 20, and the pellets 11 from the preliminary hopper 31 to the main hopper 32. And a transport part 33 for transporting the The transport unit 33 includes a cylindrical body 35 that rotatably holds the feed screw 34 and a motor 36 that rotationally drives the feed screw 34. By rotating and driving the feed screw 34 by the motor 36, the pellet 11 dropped and supplied from the preliminary hopper 31 is conveyed and supplied into the main hopper 32.
- the feeder 30 can adjust the supply amount of the composition 11 by adjusting the rotation speed of the feed screw 34.
- the transport unit 33 can transport the pellet 11 by applying a coil type, a belt type, a vibration type, pneumatic transportation, piston transportation, and other methods in addition to the illustrated screw type.
- a weight-type quantitative feeder can also be suitably used for the transport unit 33.
- the main hopper 32 can be appropriately provided with a decompression unit or an inert gas introduction unit.
- heaters 41, 42, and 43 for applying heat for melting the pellet 11 are provided.
- the heaters 41, 42, and 43 are provided corresponding to the feed zone C1, the transfer zone C2, and the metering zone C3 of the screw 21, respectively.
- band heaters that are electric heaters with easy temperature control are used.
- a type of heater that circulates the heat medium can also be used.
- tip portions of temperature sensors 61, 62, 63 such as thermocouples are embedded in the wall surface of the barrel 23. The tips of the temperature sensors 61, 62, 63 can be attached in close contact with the surface of the barrel 23.
- the wall surface temperature of the barrel 23 is maintained at the set temperature.
- the set temperature varies depending on the degree of polymerization of the material contained in the composition 11, the type of plasticizer and the amount added, but is, for example, 160 to 170 ° C.
- the die 50 has a passage through which the molten composition 11 extruded from the extruder 20 passes.
- the opening shape of the tip portion of the die 50 has a shape that matches the shape of the medical molded article 12.
- a proximal end portion of the die 50 is connected to a distal end portion of the extruder 20.
- Die heaters 44 and 45 for applying heat to the molten composition 11 extruded from the extruder 20 are also provided at the proximal end and the distal end of the die 50. Similar to the heaters 41, 42, and 43 provided in the barrel 23, band heaters are also used for the die heaters 44 and 45.
- band heaters are also used for the die heaters 44 and 45.
- tip portions of temperature sensors 64 and 65 such as thermocouples are embedded in the wall surface of the die 50. The tip portions of the temperature sensors 64 and 65 can be attached in close contact with the surface of the die 50.
- the wall surface temperature of the die 50 is maintained at a set temperature by performing on / off control of energization to the band heaters 44 and 45.
- the set temperature is, for example, 160 to 170 ° C.
- the extrusion molding apparatus 10 further includes a controller 70 that controls the operation of the extruder 20 and the feeder 30.
- the operation of the feeder 30 is controlled by the controller 70, and the supply amount of the composition 11 formed in a solid state is adjusted to an amount that does not cause the composition 11 to generate shear heat in the extruder 20.
- the operation of the extruder 20 is controlled by the controller 70, and the number of rotations of the screw 21 is adjusted.
- the screw 21 in which the depth d of the groove 22 is formed to the same depth is used.
- the feeder 30 adjusts the rotation speed of the feed screw 34 to adjust the solid composition 11 to a quantity that does not cause shearing heat generation in the composition 11 in the extruder 20. Supply. For this reason, it is suppressed that the composition 11 stays in the extruder 20, and furthermore, it is suppressed that the composition 11 is excessively sheared and heated in the extruder 20. Therefore, it is possible to suppress two factors that cause burns of the molded product.
- the “amount that does not cause shearing heat generation in the composition 11 in the extruder 20” means that the amount of the composition 11 supplied is determined in relation to the depth d of the groove 22 of the screw 21. This means an amount that can prevent the composition 11 from staying in the tube 20 and further prevent the composition 11 from excessively generating heat in the extruder 20. Therefore, even if the amount of shearing heat generated in the composition 11 is a certain amount, as long as excessive shearing heat generation that causes burning is not generated, the “amount of amount of shearing heat generation in the composition 11” is “extrusion”. It should be understood that it is included in the “amount that does not cause the composition 11 to generate a shear heating in the machine 20”.
- the temperature of the composition 11 in the extruder 20 is “set temperature + 5 ° C. or less”, more preferably “set temperature + 2 ° C. or less”. It is preferable to control the supply amount of the composition 11 by the feeder 30 so as to become. This is because it is possible to reliably suppress excessive shearing heat generation that causes burning of the molded product.
- the temperature of the composition 11 in the extruder 20 can be easily confirmed by the temperature sensors 61, 62, 63.
- composition 11 containing is formed into a solid pellet 11.
- the wall surface temperature of the barrel 23 and the wall surface temperature of the die 50 are raised to the set temperature by on / off control of energization to the heaters 41, 42, 43 and the die heaters 44, 45.
- the feeder 30 supplies the pellet 11 to the screw 21 of the extruder 20 in which the depth d of the groove 22 is formed to the same depth. At this time, the feeder 30 supplies the pellets 11 by adjusting the rotation speed of the feed screw 34 so that the pellets 11 are adjusted to an amount that does not cause shearing heat generation in the composition 11 in the extruder 20.
- the pellet 11 supplied to the screw 21 is melted by applying heat from the heaters 41, 42, 43.
- the melted composition 11 reaches the tip of the screw 21 through the groove 22 of the screw 21, since the induction by the groove 22 is lost, the forward force is weakened. Since the advance of the molten composition 11 is suppressed, the pressure of the molten composition 11 is slightly increased in the metering zone C3. However, this increase in pressure does not cause the composition 11 to generate shear heat.
- the molten composition 11 extruded from the extruder 20 is molded into the shape of the medical molded article 12 by the die 50.
- the wall surface temperature of the barrel 23 and the wall surface temperature of the die 50 are maintained at the set temperature by on / off control of energization to the heaters 41, 42, 43 and the die heaters 44, 45.
- the screw 21 formed with the same depth d of the groove 22 is used, and the composition formed into a solid form is further used.
- the product 11 is supplied in the extruder 20 at a supply amount adjusted to an amount that does not cause shearing heat generation in the composition 11. For this reason, it is suppressed that the composition 11 stays in the extruder 20, and furthermore, it is suppressed that the composition 11 is excessively sheared and heated in the extruder 20.
- low-colored (high whiteness and low yellowness) medical molded products 12 are manufactured at low cost even with a small amount of metal soap. it can.
- the temperature of the composition 11 in the extruder 20 is set to “set temperature + 5 ° C. or less”. By constituting in this way, excessive shearing heat generation that causes burning of the molded product is surely suppressed, and even with a small amount of metal soap, the degree of coloring is low (high whiteness and low yellowness). )
- the medical molded article 12 can be manufactured at a low cost.
- the extrusion apparatus 10 for forming a tube as the medical molded article 12 has been described, the present invention is not limited to this case.
- the extrusion molding apparatus 10 can be appropriately modified and applied.
- Example 1 Polyvinyl chloride resin (manufactured by Kaneka Corporation, KS-1700, average polymerization degree: 1700) 100 kg, ester plasticizer bis (2-ethylhexyl) phthalate (DEHP) 52 kg, epoxy plasticizer epoxidized soybean oil (Co., Ltd.) ADEKA, O-130P) 8 kg, Ca—Zn stabilizer as a stabilizer (manufactured by ADEKA, trade name: ADK STAB 37, calcium stearate content: about 7.57% by mass, zinc stearate content: about 10.
- this polyvinyl chloride resin composition is formed into pellets, and a tube having an inner diameter of ⁇ 3.0 mm and an outer diameter of ⁇ 4.4 mm is extrusion-molded using the above-described medical molding product extrusion molding apparatus.
- the pellets used had a spherical shape with a diameter of 3-4 mm, and the supply rate was set to 4 kg / hr.
- the inner diameter of the barrel of the extruder is 22 mm.
- the rotational speed of the screw was set to 50 rpm.
- pellets were supplied to an extruder screw formed to have the same groove depth at a supply amount adjusted so as not to cause shearing heat generation in the composition in the extruder.
- the pellets supplied to the screw were melted by applying heat from a heater, and the molten composition extruded from the extruder was formed into a tube shape by a die.
- the set temperature of the heater was 160 ° C. for the heater 41 and 170 ° C. for the heaters 42 to 45.
- the tube of this example shows high whiteness and low yellowness even with a small amount of stabilizer (zinc soap and calcium soap).
- Example 2 A tube was produced in the same manner as in Example 1 except that the amount of Ca—Zn stabilizer (trade name: ADK STAB 37 manufactured by ADEKA Corporation) was changed to 0.21 kg.
- Ca—Zn stabilizer trade name: ADK STAB 37 manufactured by ADEKA Corporation
- the tube of this example shows high whiteness and low yellowness even with a small amount of stabilizer (zinc soap and calcium soap).
- Example 3 A tube was produced in the same manner as in Example 1 except that the compounding amount of the Ca—Zn stabilizer (manufactured by ADEKA Corporation, trade name: ADK STAB 37) was changed to 0.35 kg.
- the compounding amount of the Ca—Zn stabilizer manufactured by ADEKA Corporation, trade name: ADK STAB 37
- the tube of this example shows high whiteness and low yellowness even with a small amount of stabilizer (zinc soap and calcium soap).
- Example 4 A tube was produced in the same manner as in Example 1, except that the amount of Ca—Zn stabilizer (trade name: ADK STAB 37 manufactured by ADEKA Corporation) was changed to 0.70 kg.
- Ca—Zn stabilizer trade name: ADK STAB 37 manufactured by ADEKA Corporation
- the tube of this example shows high whiteness and low yellowness even with a small amount of stabilizer (zinc soap and calcium soap).
- Extrusion molding equipment for medical molded products 11 pellets (composition), 12 Tube (medical product), 20 extruder, 21 screws, 22 grooves, 23 barrels, 30 Feeder, 34 Feed screw, 41, 42, 43 heater, 44, 45 Die heater, 50 dies, 61, 62, 63 Temperature sensor, 64, 65 temperature sensor, 70 controller, C1 feed zone, C2 transfer zone, C3 metering zone, d Groove depth.
Abstract
[Problem] To provide a technology whereby a hardly colored molded article for medical use can be manufactured at a low cost.
[Solution] A molded article for medical use that is manufactured by extrusion molding a composition, said composition comprising, per 100 parts by mass of a polyvinyl chloride resin, 30-160 parts by mass of an ester plasticizer, 5-25 parts by mass of an epoxy plasticizer, and 0.01-0.1 part by mass (in total) of a zinc soap and calcium soap, wherein the white index (W.I.) of the molded article for medical use is 25 or more and the yellow index (Y.I.) thereof is 3.5 or less. In the extrusion molding of the molded article for medical use, a composition 11 in a solid state is supplied to a screw 21 of an extruder 20, said extruder being provided with grooves 22 having the same depth d, at a rate that is regulated so as to prevent shear heat generation in the composition within the extruder. Next, the solid composition supplied to the screw is heat-melted by heaters 41, 42 and 43 and the melted composition extruded from the extruder is molded into the shape of the molded article 12 for medical use in a die 50.
Description
本発明は、医療用成形品、医療用成形品の押出成形方法、および医療用成形品の押出成形装置に関する。
The present invention relates to a medical molded article, a method for extruding a medical molded article, and an apparatus for extruding a medical molded article.
医療用材料として、従来、軟質ポリ塩化ビニル樹脂が広く使用されている。医療用具は、接触した血液が生体に戻される、生体組織中に挿入される、あるいは体力の落ちている患者付近で使用されるため、安全性がかなり配慮されている、このため、医療用具は一般的に滅菌形態で使用されるが、その滅菌方法としては、放射線滅菌、エチレンオキサイド滅菌または高圧蒸気滅菌が一般的に採用されている。その中でも放射線滅菌は、エチレンオキサイド滅菌のようにエチレンオキサイドガスの残留の心配がなく、高圧蒸気滅菌のように医療器具が高温に晒されることがないため、衛生的で医療材料にダメージの小さい優れた滅菌方法として採用されている。
Conventionally, soft polyvinyl chloride resin has been widely used as a medical material. Medical devices are used in the vicinity of patients whose contacted blood is returned to the living body, inserted into living tissue, or who are weak, so the safety is considerably considered. Generally, it is used in a sterilized form, and radiation sterilization, ethylene oxide sterilization, or high-pressure steam sterilization is generally adopted as the sterilization method. Among them, radiation sterilization is hygienic and has little damage to medical materials because there is no concern about residual ethylene oxide gas like ethylene oxide sterilization, and medical instruments are not exposed to high temperatures like high-pressure steam sterilization. It has been adopted as a sterilization method.
その一方で、軟質ポリ塩化ビニル樹脂組成物で作られた医療用具は、放射線や加熱により軟質ポリ塩化ビニル樹脂またはその配合剤が劣化／変性して、着色の促進等の不具合が発生する。
On the other hand, in medical devices made of a soft polyvinyl chloride resin composition, the soft polyvinyl chloride resin or a compounding agent thereof deteriorates / denaturates due to radiation or heating, causing problems such as promotion of coloring.
上記課題を鑑みて、特許文献１では、電子線滅菌時でも変色しにくい成形品が報告される。上記特許文献１では、３価以上の多価アルコールの３－メルカプトプロピオン酸エステルを特定量含むポリ塩化ビニル樹脂組成物で成形することを特徴としている。
In view of the above problems, Patent Document 1 reports a molded product that hardly discolors even during electron beam sterilization. Patent Document 1 is characterized in that it is molded from a polyvinyl chloride resin composition containing a specific amount of a 3-mercaptopropionic acid ester of a trihydric or higher polyhydric alcohol.
上記特許文献１に記載の成形品はたしかに電子線滅菌に対する耐変色性に優れ、電子線滅菌後に変色しにくい成形品である。
The molded article described in Patent Document 1 is certainly a molded article that is excellent in resistance to discoloration against electron beam sterilization and hardly discolors after electron beam sterilization.
一方で、ポリ塩化ビニル樹脂製の医療用成形品は汎用品であり、他の高機能医療用具に比して安価に製造することが望まれている。このため、コスト削減を考慮すると、配合剤（添加剤）の種類や量を可能な限り低減することが望まれる。
On the other hand, a medical molded product made of polyvinyl chloride resin is a general-purpose product and is desired to be manufactured at a lower cost than other high-performance medical devices. For this reason, in consideration of cost reduction, it is desired to reduce the type and amount of the compounding agent (additive) as much as possible.
したがって、本発明は、上記事情を鑑みてなされたものであり、着色（変色）を低減した医療用成形品を安価に製造できる技術を提供することを目的とする。
Therefore, the present invention has been made in view of the above circumstances, and an object of the present invention is to provide a technique capable of inexpensively manufacturing a medical molded product with reduced coloring (discoloration).
本発明者は、上記の問題を解決すべく、鋭意研究を行った結果、熱安定剤である金属石鹸量を低減しても着色度の低い（白色度が高くかつ黄色度が低い）ポリ塩化ビニル樹脂製医療用成形品を製造する技術を見出し、本発明を完成するにいたった。
As a result of intensive studies to solve the above problems, the present inventor has found that the degree of coloration is low (high whiteness and low yellowness) even when the amount of metal soap that is a heat stabilizer is reduced. The inventors have found a technique for producing a vinyl resin medical molded article and have completed the present invention.
すなわち、上記諸目的は、ポリ塩化ビニル樹脂 １００質量部に対して、エステル可塑剤 ３０～１６０質量部、エポキシ可塑剤 ５～２５質量部、および亜鉛石鹸およびカルシウム石鹸 ０．０１～０．１質量部（合計量）と含む組成物を押出成形されてなり、白色度（Ｗ．Ｉ．）が２５以上でかつ黄色度（Ｙ．Ｉ．）が３．５以下である、医療用成形品によって達成される。
That is, the above-mentioned purposes are based on 100 parts by mass of polyvinyl chloride resin, 30 to 160 parts by mass of ester plasticizer, 5 to 25 parts by mass of epoxy plasticizer, and 0.01 to 0.1 mass of zinc soap and calcium soap. A molded product for medical use which is formed by extrusion molding a composition containing a part (total amount) and has a whiteness (WI) of 25 or more and a yellowness (YI) of 3.5 or less. Achieved.
上記目的を達成する医療用成形品の押出成形方法は、上記の組成物を押出成形し、白色度（Ｗ．Ｉ．）が２５以上でかつ黄色度（Ｙ．Ｉ．）が３．５以下である医療用成形品を成形する押出成形方法である。まず、溝の深さが同じ深さに形成された押出機のスクリューに、固形状に形成した前記組成物を、前記押出機内において前記組成物に剪断発熱を生じさせない量に調整した供給量にて供給する。前記スクリューに供給された固形状の前記組成物にヒーターからの熱を加えて溶融する。そして、前記押出機から押し出された溶融状態の前記組成物をダイによって医療用成形品の形状に成形する。
A method for extruding a medical molded article that achieves the above-described object is to extrude the above-described composition and have a whiteness (WI) of 25 or more and a yellowness (YI) of 3.5 or less. This is an extrusion molding method for molding a medical molded product. First, the composition formed in a solid state on the screw of an extruder formed with the same groove depth is adjusted to a supply amount adjusted so as not to generate shear heat generation in the composition in the extruder. And supply. The solid composition supplied to the screw is melted by applying heat from a heater. And the said composition of the molten state extruded from the said extruder is shape | molded by the die | dye in the shape of a medical molded product.
上記目的を達成する医療用成形品の押出成形装置は、上記の組成物を押出成形し、白色度（Ｗ．Ｉ．）が２５以上でかつ黄色度（Ｙ．Ｉ．）が３．５以下である医療用成形品を成形する押出成形装置である。押出成形装置は、溝の深さが同じ深さに形成されたスクリューをバレル内に回転駆動自在に配置した押出機と、固形状に形成した前記組成物を前記スクリューに供給するとともに前記組成物の供給量を調整自在なフィーダーと、前記スクリューに供給された固形状の前記組成物を溶融させる熱を加えるヒーターと、前記押出機から押し出された溶融状態の前記組成物を医療用成形品の形状に成形するダイと、を有する。そして、前記フィーダーは、前記組成物の供給量を、前記押出機内において前記組成物に剪断発熱を生じさせない量に調整する。
An apparatus for extruding a medical molded article that achieves the above-described object extrudes the above-described composition and has a whiteness (WI) of 25 or more and a yellowness (YI) of 3.5 or less. This is an extrusion molding apparatus for molding a medical molded product. The extrusion molding apparatus includes an extruder in which a screw formed with the same groove depth is rotatably disposed in a barrel, and supplies the composition formed in a solid state to the screw and the composition. A feeder capable of adjusting the supply amount of the metal, a heater for applying heat to melt the solid composition supplied to the screw, and the molten composition extruded from the extruder, And a die that is formed into a shape. And the said feeder adjusts the supply amount of the said composition to the quantity which does not produce a shearing heat_generation | fever in the said composition in the said extruder.
本発明の医療用成形品は、少ない量の金属石鹸であっても着色度は低い（白色度が高くかつ黄色度が低い）。ゆえに、本発明の医療用成形品は低コストで製造できる。
The medical molded article of the present invention has a low degree of coloring (high whiteness and low yellowness) even with a small amount of metal soap. Therefore, the medical molded article of the present invention can be manufactured at low cost.
本発明の医療用成形品の押出成形技術によれば、溝の深さが同じ深さに形成されたスクリューを使用し、固形状に形成した組成物を、押出機内において組成物に剪断発熱を生じさせない量に調整した供給量にて供給している。このため、押出機内において組成物が滞留することが抑えられ、さらに押出機内において組成物が過度に剪断発熱されることが抑えられる。成形品の焼けの原因となる２つの要因を抑制できる結果、少ない量の金属石鹸であっても着色度の低い（白色度が高くかつ黄色度が低い）医療用成形品を低コストに製造できる。
According to the extrusion molding technique for a medical molded article of the present invention, a screw formed with the same groove depth is used, and a composition formed into a solid state is subjected to shear heat generation in the composition in an extruder. Supply is made with a supply amount adjusted to an amount that does not occur. For this reason, it is suppressed that a composition stagnates in an extruder, and also it is suppressed that a composition heat-extracts excessively in an extruder. As a result of suppressing two factors that cause burns in molded products, even with a small amount of metal soap, it is possible to produce medical molded products with low coloring (high whiteness and low yellowness) at low cost. .
本発明の第一は、ポリ塩化ビニル樹脂 １００質量部に対して、エステル可塑剤 ３０～１６０質量部、エポキシ可塑剤 ５～２５質量部、および亜鉛石鹸およびカルシウム石鹸 ０．０１～０．１質量部（合計量）と含む組成物を押出成形されてなり、白色度（Ｗ．Ｉ．）が２５以上でかつ黄色度（Ｙ．Ｉ．）が３．５以下である、医療用成形品を提供する。
The first of the present invention is based on 100 parts by mass of polyvinyl chloride resin, 30 to 160 parts by mass of ester plasticizer, 5 to 25 parts by mass of epoxy plasticizer, and 0.01 to 0.1 mass of zinc soap and calcium soap. A medical molded article obtained by extrusion molding of a composition containing parts (total amount) and having a whiteness (WI) of 25 or more and a yellowness (YI) of 3.5 or less. provide.
上記構成を満たす医療用成形品は、少ない量の金属石鹸であっても着色度は低い（白色度が高くかつ黄色度が低い）。ゆえに、本発明の医療用成形品は低コストで製造できる。
A medical molded article satisfying the above configuration has a low degree of coloring (high whiteness and low yellowness) even with a small amount of metal soap. Therefore, the medical molded article of the present invention can be manufactured at low cost.
一般的に、汎用型の医療用ポリ塩化ビニル樹脂製の成形品は、輸液、輸血用のバッグ、連結用チューブなど、様々な用途に使用される。この際、成形品内容物（例えば、血液、栄養剤等）の状態（例えば、液体の流れ、色）など観察が容易であるように、成形品は黄色味が低く白色味の高いものが好まれる。このため、上記特許文献１に記載されるように、従来、様々な添加剤を用いて変色や着色を抑えることが試みられてきた。その一方で、このような汎用型の医療用成形品は、様々な用途に大量に使用されるため、安価であることが要求されている。このため、コストを低減するという観点からは、配合剤（添加剤）の種類や量は少ないことが好ましい。すなわち、医療用成形品の、着色や変色の抑制・防止と、コスト削減と、は、トレードオフの関係にある。
Generally, general-purpose medical polyvinyl chloride resin molded products are used for various applications such as infusion solutions, transfusion bags, and connecting tubes. At this time, the molded product preferably has a low yellowness and a high whiteness so that the state of the molded product content (eg, blood, nutrients, etc.) (eg, liquid flow, color) can be easily observed. It is. For this reason, as described in Patent Document 1, attempts have been made to suppress discoloration and coloring using various additives. On the other hand, such general-purpose medical molded articles are used in large quantities for various purposes, and therefore are required to be inexpensive. For this reason, it is preferable that there are few kinds and quantity of a compounding agent (additive) from a viewpoint of reducing cost. That is, there is a trade-off relationship between suppression and prevention of coloring and discoloration and cost reduction of a medical molded product.
これに対して、本発明の医療用成形品は、下記に詳述するような特定の手段で製造することによって、少ない量の安定化剤（亜鉛石鹸およびカルシウム石鹸）であっても、白色度が高くかつ黄色度の低い医療用成形品を作製することが可能になったのである。
On the other hand, the medical molded article of the present invention is produced by a specific means as described in detail below, so that even if a small amount of stabilizer (zinc soap and calcium soap) is used, the whiteness degree Therefore, it is possible to produce a medical molded product having a high yellowness and a low yellowness.
以下、本発明に係るポリ塩化ビニル樹脂組成物の構成成分を詳細に説明する。なお、本明細書において、範囲を示す「Ｘ～Ｙ」は、ＸおよびＹを含み、「Ｘ以上Ｙ以下」を意味する。また、特記しない限り、操作および物性等の測定は室温（２０～２５℃）／相対湿度４０～５０％の条件で測定する。
Hereinafter, the components of the polyvinyl chloride resin composition according to the present invention will be described in detail. In this specification, “X to Y” indicating a range includes X and Y, and means “X or more and Y or less”. Unless otherwise specified, measurement of operation and physical properties is performed under conditions of room temperature (20 to 25 ° C.) / Relative humidity 40 to 50%.
（医療用成形品）
本発明の医療用成形品は、上述したような特定の組成物（ポリ塩化ビニル樹脂組成物）を押出成形することによって製造される。また、本発明の医療用成形品は、２５以上の白色度（Ｗ．Ｉ．）および３．５以下の黄色度（Ｙ．Ｉ．）を有する。このように白色度が高くかつ着色度（黄色度）の低い成形品は、高い視認性を発揮するため、成形品（例えば、チューブ）内に液体（例えば、血液、栄養剤等）を流しても、その状態（例えば、液体の流れ、色）を良好に視認できる。 (Medical product)
The medical molded article of the present invention is produced by extruding a specific composition (polyvinyl chloride resin composition) as described above. The medical molded article of the present invention has a whiteness (WI) of 25 or more and a yellowness (YI) of 3.5 or less. In this way, a molded product having a high whiteness and a low coloration degree (yellowness) exhibits high visibility. Therefore, a liquid (for example, blood, nutrients, etc.) is poured into the molded product (for example, a tube). Moreover, the state (for example, the flow of a liquid, a color) can be visually recognized well.
本発明の医療用成形品は、上述したような特定の組成物（ポリ塩化ビニル樹脂組成物）を押出成形することによって製造される。また、本発明の医療用成形品は、２５以上の白色度（Ｗ．Ｉ．）および３．５以下の黄色度（Ｙ．Ｉ．）を有する。このように白色度が高くかつ着色度（黄色度）の低い成形品は、高い視認性を発揮するため、成形品（例えば、チューブ）内に液体（例えば、血液、栄養剤等）を流しても、その状態（例えば、液体の流れ、色）を良好に視認できる。 (Medical product)
The medical molded article of the present invention is produced by extruding a specific composition (polyvinyl chloride resin composition) as described above. The medical molded article of the present invention has a whiteness (WI) of 25 or more and a yellowness (YI) of 3.5 or less. In this way, a molded product having a high whiteness and a low coloration degree (yellowness) exhibits high visibility. Therefore, a liquid (for example, blood, nutrients, etc.) is poured into the molded product (for example, a tube). Moreover, the state (for example, the flow of a liquid, a color) can be visually recognized well.
視認性のより向上効果などを考慮すると、医療用成形品の白色度は、好ましくは２６以上、より好ましくは２７以上、特に好ましくは２８以上である。なお、医療用成形品の白色度は、高いほど好ましいため、特に上限は設定されないが、５０以下程度であれば十分である。同様にして、視認性のより向上効果などを考慮すると、医療用成形品の黄色度は、好ましくは３以下、より好ましくは２以下、特に好ましくは１．５以下である。なお、医療用成形品の黄色度は、低いほど好ましいため、特に下限は設定されず、０以上である。
Considering the effect of improving visibility, the whiteness of the medical molded product is preferably 26 or more, more preferably 27 or more, and particularly preferably 28 or more. In addition, since it is so preferable that the whiteness of a medical molded product is high, an upper limit in particular is not set, but about 50 or less is enough. Similarly, considering the effect of improving visibility and the like, the yellowness of the medical molded article is preferably 3 or less, more preferably 2 or less, and particularly preferably 1.5 or less. In addition, since the yellow degree of a medical molded product is so preferable that it is low, a minimum in particular is not set but it is 0 or more.
本明細書において、医療用成形品の白色度及び黄色度は下記方法に従って測定された値である。
In the present specification, the whiteness and yellowness of a medical molded product are values measured according to the following method.
（医療用成形品の白色度および黄色度の測定方法）
内径：３．０ｍｍ、外径：４．４ｍｍのチューブを押出成形する（サンプルチューブ）。このサンプルチューブ（ｎ＝８）について、白色度（Ｗ．Ｉ．）及び黄色度（Ｙ．Ｉ．）は、ＡＳＴＭ Ｅ３１３－７３に準拠した方法に従って、下記条件にて測定し、その平均の値を採用する。 (Measurement method of whiteness and yellowness of medical molded products)
A tube having an inner diameter of 3.0 mm and an outer diameter of 4.4 mm is extruded (sample tube). For this sample tube (n = 8), the whiteness (WI) and yellowness (YI) were measured under the following conditions according to the method in accordance with ASTM E313-73, and the average value thereof. Is adopted.
内径：３．０ｍｍ、外径：４．４ｍｍのチューブを押出成形する（サンプルチューブ）。このサンプルチューブ（ｎ＝８）について、白色度（Ｗ．Ｉ．）及び黄色度（Ｙ．Ｉ．）は、ＡＳＴＭ Ｅ３１３－７３に準拠した方法に従って、下記条件にて測定し、その平均の値を採用する。 (Measurement method of whiteness and yellowness of medical molded products)
A tube having an inner diameter of 3.0 mm and an outer diameter of 4.4 mm is extruded (sample tube). For this sample tube (n = 8), the whiteness (WI) and yellowness (YI) were measured under the following conditions according to the method in accordance with ASTM E313-73, and the average value thereof. Is adopted.
（ポリ塩化ビニル樹脂）
ポリ塩化ビニル樹脂は、特に制限されず、通常、医療用途で使用されるポリ塩化ビニル樹脂が同様にして使用される。このため、ポリ塩化ビニル樹脂は、合成品を用いてもいいし、市販品を用いてもよい。好ましくは、重合度が、１０００～２０００程度のポリ塩化ビニル樹脂を使用される。ここで、市販品の例としては、例えば、ポリ塩化ビニル樹脂 Ｓ－４００、Ｓ１００６、Ｓ１００７、Ｓ１００８、Ｓ１００１、Ｓ１００１Ｎ、Ｓ１００３、Ｓ１００３Ｎ、Ｓ１００４、ＫＳ－１７００、ＫＳ－２５００、ＫＳ－３０００（以上、株式会社カネカ製）などが挙げられる。また、ポリ塩化ビニル樹脂の合成方法としては、特に制限されないが、例えば、懸濁重合法などが挙げられる。なお、上記ポリ塩化ビニル樹脂は、単独で用いてもよいし、２種以上を組み合わせて用いてもよい。 (Polyvinyl chloride resin)
The polyvinyl chloride resin is not particularly limited, and a polyvinyl chloride resin usually used for medical purposes is used in the same manner. For this reason, as the polyvinyl chloride resin, a synthetic product or a commercially available product may be used. Preferably, a polyvinyl chloride resin having a degree of polymerization of about 1000 to 2000 is used. Here, as examples of commercially available products, for example, polyvinyl chloride resins S-400, S1006, S1007, S1008, S1001, S1001N, S1003, S1003N, S1004, KS-1700, KS-2500, KS-3000 (or more, Manufactured by Kaneka Corporation). The method for synthesizing the polyvinyl chloride resin is not particularly limited, and examples thereof include a suspension polymerization method. In addition, the said polyvinyl chloride resin may be used independently and may be used in combination of 2 or more type.
ポリ塩化ビニル樹脂は、特に制限されず、通常、医療用途で使用されるポリ塩化ビニル樹脂が同様にして使用される。このため、ポリ塩化ビニル樹脂は、合成品を用いてもいいし、市販品を用いてもよい。好ましくは、重合度が、１０００～２０００程度のポリ塩化ビニル樹脂を使用される。ここで、市販品の例としては、例えば、ポリ塩化ビニル樹脂 Ｓ－４００、Ｓ１００６、Ｓ１００７、Ｓ１００８、Ｓ１００１、Ｓ１００１Ｎ、Ｓ１００３、Ｓ１００３Ｎ、Ｓ１００４、ＫＳ－１７００、ＫＳ－２５００、ＫＳ－３０００（以上、株式会社カネカ製）などが挙げられる。また、ポリ塩化ビニル樹脂の合成方法としては、特に制限されないが、例えば、懸濁重合法などが挙げられる。なお、上記ポリ塩化ビニル樹脂は、単独で用いてもよいし、２種以上を組み合わせて用いてもよい。 (Polyvinyl chloride resin)
The polyvinyl chloride resin is not particularly limited, and a polyvinyl chloride resin usually used for medical purposes is used in the same manner. For this reason, as the polyvinyl chloride resin, a synthetic product or a commercially available product may be used. Preferably, a polyvinyl chloride resin having a degree of polymerization of about 1000 to 2000 is used. Here, as examples of commercially available products, for example, polyvinyl chloride resins S-400, S1006, S1007, S1008, S1001, S1001N, S1003, S1003N, S1004, KS-1700, KS-2500, KS-3000 (or more, Manufactured by Kaneka Corporation). The method for synthesizing the polyvinyl chloride resin is not particularly limited, and examples thereof include a suspension polymerization method. In addition, the said polyvinyl chloride resin may be used independently and may be used in combination of 2 or more type.
（エステル可塑剤）
本発明に係るポリ塩化ビニル樹脂組成物には、エステル可塑剤が、ポリ塩化ビニル樹脂１００質量部に対し、３０～１６０質量部、好ましくは４０～１００質量部の量で、配合されている。ここで、エステル可塑剤の配合量が１６０質量部を超えると、エステル可塑剤が均一に混合されにくくなるので、ポリ塩化ビニル樹脂組成物のコンパウンドとして製造することが困難となる場合がある。逆に、エステル可塑剤の配合量が３０質量部未満であると、ポリ塩化ビニル樹脂との相溶性が低下し、所望の柔軟性が得られず、好ましくない。 (Ester plasticizer)
In the polyvinyl chloride resin composition according to the present invention, an ester plasticizer is blended in an amount of 30 to 160 parts by mass, preferably 40 to 100 parts by mass with respect to 100 parts by mass of the polyvinyl chloride resin. Here, when the blending amount of the ester plasticizer exceeds 160 parts by mass, the ester plasticizer becomes difficult to be uniformly mixed, and thus it may be difficult to manufacture as a compound of the polyvinyl chloride resin composition. On the contrary, if the amount of the ester plasticizer is less than 30 parts by mass, the compatibility with the polyvinyl chloride resin is lowered, and the desired flexibility cannot be obtained, which is not preferable.
本発明に係るポリ塩化ビニル樹脂組成物には、エステル可塑剤が、ポリ塩化ビニル樹脂１００質量部に対し、３０～１６０質量部、好ましくは４０～１００質量部の量で、配合されている。ここで、エステル可塑剤の配合量が１６０質量部を超えると、エステル可塑剤が均一に混合されにくくなるので、ポリ塩化ビニル樹脂組成物のコンパウンドとして製造することが困難となる場合がある。逆に、エステル可塑剤の配合量が３０質量部未満であると、ポリ塩化ビニル樹脂との相溶性が低下し、所望の柔軟性が得られず、好ましくない。 (Ester plasticizer)
In the polyvinyl chloride resin composition according to the present invention, an ester plasticizer is blended in an amount of 30 to 160 parts by mass, preferably 40 to 100 parts by mass with respect to 100 parts by mass of the polyvinyl chloride resin. Here, when the blending amount of the ester plasticizer exceeds 160 parts by mass, the ester plasticizer becomes difficult to be uniformly mixed, and thus it may be difficult to manufacture as a compound of the polyvinyl chloride resin composition. On the contrary, if the amount of the ester plasticizer is less than 30 parts by mass, the compatibility with the polyvinyl chloride resin is lowered, and the desired flexibility cannot be obtained, which is not preferable.
エステル可塑剤の例としては、特に限定されないが、例えば、トリメリット酸トリ－２－エチルヘキシル（ＴＯＴＭ）等のトリメリット酸エステル；アセチルクエン酸トリブチル、アセチルクエン酸トリヘキシル、ｎ－ブチリルクエン酸トリヘキシルなどのクエン酸エステル；フタル酸ビス（２－エチルヘキシル）（ＤＥＨＰ）（フタル酸ジオクチル（ＤＯＰ））、フタル酸ジイソノニル（ＤＩＮＰ）、フタル酸ジイソデシル（ＤＩＤＰ）、フタル酸ジブチル（ＤＢＰ）等のフタル酸エステル；アジピン酸ジオクチル、アジピン酸ジイソノニル等のアジピン酸エステル；リン酸トリクレシル等のリン酸エステルなどが挙げられる。これらの中でも、柔軟性（特に低温柔軟性）、熱安定性、安全性の観点から、トリメリット酸エステルやフタル酸エステルが好ましく、ＴＯＴＭやＤＥＨＰがより好ましい。
Examples of ester plasticizers include, but are not limited to, for example, trimellitic esters such as tri-2-ethylhexyl trimellitic acid (TOTM); tributyl acetyl citrate, trihexyl acetyl citrate, trihexyl n-butyryl citrate, etc. Citric acid esters; phthalic acid esters such as bis (2-ethylhexyl) phthalate (DEHP) (dioctyl phthalate (DOP)), diisononyl phthalate (DINP), diisodecyl phthalate (DIDP), dibutyl phthalate (DBP); Examples include adipic acid esters such as dioctyl adipate and diisononyl adipate; and phosphate esters such as tricresyl phosphate. Among these, trimellitic acid ester and phthalic acid ester are preferable, and TOTM and DEHP are more preferable from the viewpoints of flexibility (particularly low temperature flexibility), thermal stability, and safety.
本発明で用いられるエステル可塑剤は、合成品を用いてもよいし、市販品を用いてもよい。市販品の例としては、例えば、ジェイ・プラス社製 ＴＯＴＭ－ＮＢが挙げられる。また、合成方法としては、例えば、無水トリメリット酸とアルコールとを混合しエステル化する方法が挙げられる。
As the ester plasticizer used in the present invention, a synthetic product or a commercially available product may be used. Examples of commercially available products include TOTM-NB manufactured by Jay Plus. Examples of the synthesis method include a method of esterifying by mixing trimellitic anhydride and alcohol.
上記エステル可塑剤は、単独で用いてもよいし、２種以上を組み合わせて用いてもよい。
The above ester plasticizers may be used alone or in combination of two or more.
（エポキシ可塑剤）
本発明に係るポリ塩化ビニル樹脂組成物には、エポキシ可塑剤が、ポリ塩化ビニル樹脂１００質量部に対し、５～２５質量部、好ましくは７～１５質量部の量で、配合されている。エポキシ可塑剤は、可塑剤兼加工助剤として作用する。また、エポキシ可塑剤は、亜鉛石鹸およびカルシウム石鹸（安定剤）の熱安定補助剤としても作用する。ここで、エポキシ可塑剤の配合量が多すぎると、細胞毒性の悪化、成形時のエポキシ可塑剤のブリードアウトが懸念される。一方、エポキシ可塑剤の配合量が少なすぎると、所望の柔軟性、耐変色性、耐熱性が低下したり、着色を誘発したりする場合がある。 (Epoxy plasticizer)
In the polyvinyl chloride resin composition according to the present invention, an epoxy plasticizer is blended in an amount of 5 to 25 parts by mass, preferably 7 to 15 parts by mass with respect to 100 parts by mass of the polyvinyl chloride resin. Epoxy plasticizers act as plasticizers and processing aids. The epoxy plasticizer also acts as a heat stabilization aid for zinc soap and calcium soap (stabilizer). Here, when there are too many compounding quantities of an epoxy plasticizer, there exists a concern about the deterioration of cytotoxicity and the bleeding out of the epoxy plasticizer at the time of shaping | molding. On the other hand, when there are too few compounding quantities of an epoxy plasticizer, desired softness | flexibility, discoloration resistance, and heat resistance may fall, or coloring may be induced.
本発明に係るポリ塩化ビニル樹脂組成物には、エポキシ可塑剤が、ポリ塩化ビニル樹脂１００質量部に対し、５～２５質量部、好ましくは７～１５質量部の量で、配合されている。エポキシ可塑剤は、可塑剤兼加工助剤として作用する。また、エポキシ可塑剤は、亜鉛石鹸およびカルシウム石鹸（安定剤）の熱安定補助剤としても作用する。ここで、エポキシ可塑剤の配合量が多すぎると、細胞毒性の悪化、成形時のエポキシ可塑剤のブリードアウトが懸念される。一方、エポキシ可塑剤の配合量が少なすぎると、所望の柔軟性、耐変色性、耐熱性が低下したり、着色を誘発したりする場合がある。 (Epoxy plasticizer)
In the polyvinyl chloride resin composition according to the present invention, an epoxy plasticizer is blended in an amount of 5 to 25 parts by mass, preferably 7 to 15 parts by mass with respect to 100 parts by mass of the polyvinyl chloride resin. Epoxy plasticizers act as plasticizers and processing aids. The epoxy plasticizer also acts as a heat stabilization aid for zinc soap and calcium soap (stabilizer). Here, when there are too many compounding quantities of an epoxy plasticizer, there exists a concern about the deterioration of cytotoxicity and the bleeding out of the epoxy plasticizer at the time of shaping | molding. On the other hand, when there are too few compounding quantities of an epoxy plasticizer, desired softness | flexibility, discoloration resistance, and heat resistance may fall, or coloring may be induced.
エポキシ可塑剤の例としては、例えば、エポキシ化大豆油、エポキシ化亜麻仁油などのエポキシ類などが挙げられる。
Examples of the epoxy plasticizer include epoxies such as epoxidized soybean oil and epoxidized linseed oil.
本発明で用いられるエポキシ可塑剤は、合成品を用いてもよいし、市販品を用いてもよい。市販品の例としては、例えば、株式会社ＡＤＥＫＡ製 Ｏ－１３０Ｐ、Ｏ－１８０Ａなどが挙げられる。また、合成方法としては、例えば、アルケンを直接エポキシ化する方法が挙げられる。
The epoxy plasticizer used in the present invention may be a synthetic product or a commercially available product. Examples of commercially available products include O-130P and O-180A manufactured by ADEKA Corporation. Examples of the synthesis method include a method of directly epoxidizing an alkene.
上記エポキシ可塑剤は、単独で用いてもよいし、２種以上を組み合わせて用いてもよい。
The above epoxy plasticizers may be used alone or in combination of two or more.
（亜鉛石鹸およびカルシウム石鹸）
本発明に係るポリ塩化ビニル樹脂組成物には、亜鉛石鹸およびカルシウム石鹸が、ポリ塩化ビニル樹脂１００質量部に対し、安定剤として、これらの合計量として、０．０１～０．１質量部、好ましくは０．０３～０．０８質量部の量で、配合されている。ここで、上記配合量が多すぎると、ポリ塩化ビニル樹脂組成物の透明性が低下する。また、ポリ塩化ビニル樹脂の滅菌後の着色が増大する傾向にある。一方、配合量が少なすぎると、耐熱性、耐変色性が低下したり、着色を誘発したりしうる。 (Zinc soap and calcium soap)
In the polyvinyl chloride resin composition according to the present invention, zinc soap and calcium soap are used as a stabilizer with respect to 100 parts by mass of the polyvinyl chloride resin as a total of 0.01 to 0.1 parts by mass, The amount is preferably 0.03 to 0.08 parts by mass. Here, when there is too much the said compounding quantity, the transparency of a polyvinyl chloride resin composition will fall. In addition, the coloration of the polyvinyl chloride resin after sterilization tends to increase. On the other hand, if the blending amount is too small, heat resistance and discoloration resistance may be lowered, or coloring may be induced.
本発明に係るポリ塩化ビニル樹脂組成物には、亜鉛石鹸およびカルシウム石鹸が、ポリ塩化ビニル樹脂１００質量部に対し、安定剤として、これらの合計量として、０．０１～０．１質量部、好ましくは０．０３～０．０８質量部の量で、配合されている。ここで、上記配合量が多すぎると、ポリ塩化ビニル樹脂組成物の透明性が低下する。また、ポリ塩化ビニル樹脂の滅菌後の着色が増大する傾向にある。一方、配合量が少なすぎると、耐熱性、耐変色性が低下したり、着色を誘発したりしうる。 (Zinc soap and calcium soap)
In the polyvinyl chloride resin composition according to the present invention, zinc soap and calcium soap are used as a stabilizer with respect to 100 parts by mass of the polyvinyl chloride resin as a total of 0.01 to 0.1 parts by mass, The amount is preferably 0.03 to 0.08 parts by mass. Here, when there is too much the said compounding quantity, the transparency of a polyvinyl chloride resin composition will fall. In addition, the coloration of the polyvinyl chloride resin after sterilization tends to increase. On the other hand, if the blending amount is too small, heat resistance and discoloration resistance may be lowered, or coloring may be induced.
亜鉛石鹸としては、特に限定されないが、ラウリン酸亜鉛、パルミチン酸亜鉛、ステアリン酸亜鉛およびオレイン酸亜鉛のようなラウリル基、パルミチル基、ステアリル基またはオレイル基を含むものが好ましく用いられる。このようなアルキル基を有するものは、安全性の観点から医療用途に好適である。
The zinc soap is not particularly limited, but those containing lauryl group, palmityl group, stearyl group or oleyl group such as zinc laurate, zinc palmitate, zinc stearate and zinc oleate are preferably used. Those having such an alkyl group are suitable for medical use from the viewpoint of safety.
本発明で用いられる亜鉛石鹸は、合成品を用いてもよいし、市販品を用いてもよい。市販品の例としては、例えば、堺化学工業株式会社製のステアリン酸亜鉛が挙げられる。また、亜鉛石鹸を合成するための合成方法としては、例えば、脂肪酸のアルカリ金属塩水溶液と、無機金属塩とを複分解反応させる方法が挙げられる。
The zinc soap used in the present invention may be a synthetic product or a commercial product. As an example of a commercial item, the zinc stearate by Sakai Chemical Industry Co., Ltd. is mentioned, for example. Examples of the synthesis method for synthesizing zinc soap include a method in which an aqueous solution of an alkali metal salt of a fatty acid and an inorganic metal salt are subjected to a metathesis reaction.
また、カルシウム石鹸としては、特に制限されないが、上記亜鉛石鹸と同様に、ラウリン酸カルシウム、パルミチン酸カルシウム、ステアリン酸カルシウム、またはオレイン酸カルシウムのようなラウリル基、パルミチル基、ステアリル基またはオレイル基を含むものが好ましく用いられる。このようなアルキル基を有するものは、安全性の面から特に医療用途に好適である。
In addition, the calcium soap is not particularly limited, but, like the zinc soap, contains a lauryl group such as calcium laurate, calcium palmitate, calcium stearate, or calcium oleate, a palmityl group, a stearyl group, or an oleyl group. Is preferably used. Those having such an alkyl group are particularly suitable for medical use from the viewpoint of safety.
本発明で用いられるカルシウム石鹸は、合成品を用いてもよいし、市販品を用いてもよい。市販品の例としては、例えば、堺化学工業株式会社製のステアリン酸カルシウムが挙げられる。また、カルシウム石鹸を合成するための合成方法としては、例えば脂肪酸のアルカリ金属塩水溶液と無機金属塩とで複分解反応させる方法が挙げられる。
The calcium soap used in the present invention may be a synthetic product or a commercially available product. Examples of commercially available products include calcium stearate manufactured by Sakai Chemical Industry Co., Ltd. Moreover, as a synthesis method for synthesizing calcium soap, for example, a method of metathesis reaction between an aqueous solution of an alkali metal salt of a fatty acid and an inorganic metal salt can be mentioned.
上記亜鉛石鹸およびカルシウム石鹸は、それぞれ、単独で用いてもよいし、２種以上を組み合わせて用いてもよい。
The zinc soap and calcium soap may be used alone or in combination of two or more.
本発明に係るポリ塩化ビニル樹脂組成物は、亜鉛石鹸およびカルシウム石鹸を含む。ここで、亜鉛石鹸およびカルシウム石鹸の混合割合は、特に制限されないが、好ましくは亜鉛石鹸およびカルシウム石鹸の混合比（亜鉛石鹸：カルシウム石鹸の質量比）は、好ましくは１：１～３、より好ましくは１：１～２である。このような混合比であれば、着色を有意に低減でき、白色度がより高くかつ黄色度がより低い医療用成形品がより安価に製造できる。
The polyvinyl chloride resin composition according to the present invention contains zinc soap and calcium soap. Here, the mixing ratio of zinc soap and calcium soap is not particularly limited, but preferably the mixing ratio of zinc soap and calcium soap (mass ratio of zinc soap: calcium soap) is preferably 1: 1 to 3, more preferably. Is 1: 1-2. With such a mixing ratio, coloring can be significantly reduced, and a molded product for medical use having higher whiteness and lower yellowness can be produced at a lower cost.
亜鉛石鹸およびカルシウム石鹸は、ポリ塩化ビニル樹脂組成物にそれぞれ別個に配合されてもよいが、所定の割合で予め配合された混合物を配合してもよい。後者の場合、混合物は、市販品を使用してもよい。市販品の例としては、例えば、安定剤 アデカスタブシリーズ ＳＣ－１２、５９３、３７、ＳＣ－３０８Ｅ（以上、株式会社ＡＤＥＫＡ製）などが挙げられる。
Zinc soap and calcium soap may be blended separately in the polyvinyl chloride resin composition, but a mixture blended in advance at a predetermined ratio may be blended. In the latter case, a commercially available product may be used as the mixture. Examples of commercially available products include, for example, stabilizers ADEKA STAB series SC-12, 593, 37, SC-308E (manufactured by ADEKA Corporation).
（その他の成分）
本発明の成形品を形成するポリ塩化ビニル樹脂組成物は、本発明の目的を達成でき、本来の特性を特に損なわない限り、さらに他の任意成分を配合させることもできる。これら任意成分とは、例えば、金属酸化物、耐熱性向上剤、滑剤、顔料、界面活性剤、加工助剤等が挙げられる。 (Other ingredients)
The polyvinyl chloride resin composition forming the molded article of the present invention can achieve the object of the present invention, and can further contain other optional components as long as the original characteristics are not particularly impaired. Examples of these optional components include metal oxides, heat resistance improvers, lubricants, pigments, surfactants, and processing aids.
本発明の成形品を形成するポリ塩化ビニル樹脂組成物は、本発明の目的を達成でき、本来の特性を特に損なわない限り、さらに他の任意成分を配合させることもできる。これら任意成分とは、例えば、金属酸化物、耐熱性向上剤、滑剤、顔料、界面活性剤、加工助剤等が挙げられる。 (Other ingredients)
The polyvinyl chloride resin composition forming the molded article of the present invention can achieve the object of the present invention, and can further contain other optional components as long as the original characteristics are not particularly impaired. Examples of these optional components include metal oxides, heat resistance improvers, lubricants, pigments, surfactants, and processing aids.
これらのうち、金属酸化物としては、特に制限されないが、例えば、酸化マグネシウム、酸化カルシウム、酸化亜鉛等が挙げられる。
Among these, the metal oxide is not particularly limited, and examples thereof include magnesium oxide, calcium oxide, and zinc oxide.
耐熱性向上剤としては、特に制限されないが、例えば、ペンタエリスリトール類、ハイドロタルサイト等が挙げられる。
The heat resistance improver is not particularly limited, and examples thereof include pentaerythritols and hydrotalcite.
滑剤としては、特に制限されないが、例えば、シリコーンオイル等が挙げられる。
The lubricant is not particularly limited, and examples thereof include silicone oil.
顔料としては、特に制限されないが、例えば、金属錯塩系顔料等が挙げられる。
The pigment is not particularly limited, and examples thereof include metal complex pigments.
界面活性剤としては、特に制限されないが、例えば、ステアリン酸モノグリセライド等が挙げられる。
The surfactant is not particularly limited, and examples thereof include stearic acid monoglyceride.
加工助剤としては、特に制限されないが、例えば、アクリル系高分子加工助剤等が挙げられる。
The processing aid is not particularly limited, and examples thereof include acrylic polymer processing aids.
これら配合剤の配合量は、ポリ塩化ビニル樹脂組成物としての安全性、耐熱性、および耐着色性を損なわない範囲であれば、特に制限されるものではない。好ましくは、これらの配合剤の配合量の合計は、本発明に係るポリ塩化ビニル樹脂組成物１００質量部に対して、好ましくは０．１～０．５質量部である。
The compounding amounts of these compounding agents are not particularly limited as long as they do not impair the safety, heat resistance, and coloring resistance of the polyvinyl chloride resin composition. Preferably, the total amount of these compounding agents is preferably 0.1 to 0.5 parts by mass with respect to 100 parts by mass of the polyvinyl chloride resin composition according to the present invention.
本発明に係るポリ塩化ビニル樹脂組成物は、特に制限されず、上記ポリ塩化ビニル樹脂組成物を押出成形することによって製造される。
The polyvinyl chloride resin composition according to the present invention is not particularly limited, and is produced by extruding the polyvinyl chloride resin composition.
（医療用成形品の押出成形方法、およびその装置）
次に、少ない量の安定化剤であっても、白色度が高くかつ黄色度の低い医療用成形品を作製することが可能な押出成形方法、およびその押出成形方具現化した押出成形装置１０について説明する。 (Method and apparatus for extrusion molding of medical molded product)
Next, an extrusion molding method capable of producing a medical molded article having high whiteness and low yellowness even with a small amount of stabilizer, and anextrusion molding apparatus 10 embodying the extrusion molding method. Will be described.
次に、少ない量の安定化剤であっても、白色度が高くかつ黄色度の低い医療用成形品を作製することが可能な押出成形方法、およびその押出成形方具現化した押出成形装置１０について説明する。 (Method and apparatus for extrusion molding of medical molded product)
Next, an extrusion molding method capable of producing a medical molded article having high whiteness and low yellowness even with a small amount of stabilizer, and an
以下、図面を参照して、実施の形態を説明する。なお、図面の寸法比率は、説明の都合上、誇張されて実際の比率とは異なる場合がある。
Hereinafter, embodiments will be described with reference to the drawings. In addition, the dimension ratio of drawing is exaggerated on account of description, and may differ from an actual ratio.
図１は、本発明の実施形態に係る医療用成形品の押出成形装置１０を示す概略構成図、図２は、図１に示す医療用成形品の押出成形装置１０の要部を示す断面図である。
FIG. 1 is a schematic configuration diagram illustrating an extrusion molding apparatus 10 for a medical molded product according to an embodiment of the present invention, and FIG. 2 is a cross-sectional view illustrating a main part of the extrusion molding apparatus 10 for a medical molded product illustrated in FIG. It is.
図１、図２を参照して、本実施形態の押出成形装置１０は、概説すると、上述した組成物１１を押出成形し、白色度（Ｗ．Ｉ．）が２５以上でかつ黄色度（Ｙ．Ｉ．）が３．５以下である医療用成形品１２としての例えばチューブを成形する。押出成形装置１０は、溝２２の深さｄが同じ深さに形成されたスクリュー２１をバレル２３内に回転駆動自在に配置した押出機２０と、固形状に形成した組成物１１をスクリュー２１に供給するとともに組成物１１の供給量を調整自在なフィーダー３０と、スクリュー２１に供給された固形状の組成物１１を溶融させる熱を加えるヒーター４１、４２、４３と、押出機２０から押し出された溶融状態の組成物１１を医療用成形品１２の形状に成形するダイ５０と、を有している。そして、フィーダー３０は、組成物１１の供給量を、押出機２０内において組成物１１に剪断発熱を生じさせない量に調整する。この医療用成形品の押出成形装置１０にあっては、溝２２の深さｄが同じ深さに形成された押出機２０のスクリュー２１に、固形状に形成した組成物１１を、押出機２０内において組成物１１に剪断発熱を生じさせない量に調整した供給量にて供給する。そして、スクリュー２１に供給された固形状の組成物１１にヒーター４１、４２、４３からの熱を加えて溶融し、押出機２０から押し出された溶融状態の組成物１１をダイ５０によって医療用成形品１２の形状に成形している。以下、詳述する。
With reference to FIG. 1 and FIG. 2, the extrusion molding apparatus 10 of the present embodiment can be summarized as follows. The composition 11 described above is extruded, and the whiteness (WI) is 25 or more and the yellowness (Y ..I.), For example, a tube as the medical molded article 12 having a value of 3.5 or less. The extrusion molding apparatus 10 includes an extruder 20 in which a screw 21 in which the depth d of the groove 22 is formed to the same depth is rotatably disposed in a barrel 23, and a composition 11 formed in a solid form in the screw 21. Feeder 30 capable of supplying and adjusting the supply amount of composition 11, heaters 41, 42, 43 for applying heat to melt solid composition 11 supplied to screw 21, and extruded from extruder 20 And a die 50 for molding the molten composition 11 into the shape of the medical molded article 12. Then, the feeder 30 adjusts the supply amount of the composition 11 to an amount that does not cause the composition 11 to generate shear heat in the extruder 20. In the extrusion molding apparatus 10 for a medical molded article, the composition 11 formed in a solid form is applied to the screw 21 of the extruder 20 in which the depth d of the groove 22 is formed to the same depth. The composition 11 is supplied at a supply amount adjusted so as not to cause shearing heat generation. Then, the solid composition 11 supplied to the screw 21 is melted by applying heat from the heaters 41, 42, 43, and the molten composition 11 extruded from the extruder 20 is molded by the die 50 for medical use. The shape of the product 12 is formed. Details will be described below.
組成物１１は、上述したとおり、ポリ塩化ビニル樹脂 １００質量部に対して、エステル可塑剤 ３０～１６０質量部、エポキシ可塑剤 ５～２５質量部、および亜鉛石鹸およびカルシウム石鹸 ０．０１～０．１質量部（合計量）を含んでいる。組成物１１は、固形状のペレットに形成される。ペレット１１（組成物）は、図示しない除湿乾燥機において加熱乾燥されている。ペレット１１は、樹脂メーカー推奨の乾燥条件にて樹脂メーカー指定の含水率に保たれている。ペレット１１は、例えば、φ３～４ｍｍの球形形状を有する。ペレット１１の形状は球形形状に限られるものではなく、たとえば、短い棒形状を有していてもよい。
As described above, the composition 11 has an ester plasticizer of 30 to 160 parts by mass, an epoxy plasticizer of 5 to 25 parts by mass, and zinc soap and calcium soap of 0.01 to 0.00 per 100 parts by mass of the polyvinyl chloride resin. 1 part by mass (total amount) is included. The composition 11 is formed into a solid pellet. The pellet 11 (composition) is heat-dried in a dehumidifying dryer (not shown). The pellet 11 is kept at the moisture content specified by the resin manufacturer under the drying conditions recommended by the resin manufacturer. The pellet 11 has a spherical shape with a diameter of 3 to 4 mm, for example. The shape of the pellet 11 is not limited to a spherical shape, and may have a short bar shape, for example.
押出機２０は、シリンダーとも称されるバレル２３と、バレル２３内に回転可能に保持されるスクリュー２１と、スクリュー２１を回転駆動する歯車列２４やモータ２５と、を有している。バレル２３には、成形材料を投入する投入口が開口されている。スクリュー２１は、基端側から先端側に順に、フィードゾーンＣ１、移送ゾーンＣ２、およびメータリングゾーンＣ３が形成されている。スクリュー２１のフィードゾーンＣ１、およびスクリュー２１基端部がバレル２３の投入口に臨む部位によって供給部２６が構成される。二軸押出機を用いた場合は、可塑化や混練は行い易いものの、過度な剪断発熱が組成物１１に加えられ、焼けの原因となる。このため、押出機２０は、単軸押出機の方が好ましい。
The extruder 20 has a barrel 23 also called a cylinder, a screw 21 that is rotatably held in the barrel 23, and a gear train 24 and a motor 25 that rotationally drive the screw 21. The barrel 23 is opened with an inlet for feeding a molding material. In the screw 21, a feed zone C1, a transfer zone C2, and a metering zone C3 are formed in order from the proximal end side to the distal end side. The supply section 26 is configured by the feed zone C1 of the screw 21 and the portion where the base end of the screw 21 faces the charging port of the barrel 23. When a twin screw extruder is used, plasticization and kneading are easy to perform, but excessive shearing heat is added to the composition 11 and causes burning. For this reason, the extruder 20 is preferably a single-screw extruder.
スクリュー２１は、本体部２１ａと、本体部２１ａの外周面から突出するフライト部２１ｂとを有する。フライト部２１ｂは、本体部２１ａの外周面上を螺旋状に伸びている。本体部２１ａは、外径が一定寸法の直管形状を有する。フライト部２１ｂは、外径が一定寸法である。したがって、スクリュー２１は、溝２２の深さｄが同じ深さに形成されている。スクリュー２１のフィードゾーンＣ１とバレル２３内周面との間の隙間寸法、移送ゾーンＣ２とバレル２３内周面との間の隙間寸法、およびメータリングゾーンＣ３とバレル２３内周面との間の隙間寸法は、いずれも同じ寸法である。
The screw 21 has a main body part 21a and a flight part 21b protruding from the outer peripheral surface of the main body part 21a. The flight part 21b extends spirally on the outer peripheral surface of the main body part 21a. The main body 21a has a straight pipe shape with a constant outer diameter. The flight part 21b has a constant outer diameter. Therefore, the screw 21 is formed so that the depth d of the groove 22 is the same. The gap dimension between the feed zone C1 of the screw 21 and the inner peripheral surface of the barrel 23, the gap dimension between the transfer zone C2 and the inner peripheral surface of the barrel 23, and between the metering zone C3 and the inner peripheral surface of the barrel 23 The gap dimensions are all the same.
フィーダー３０は、ペレット１１がローダー（図示せず）によって供給される予備ホッパー３１と、押出機２０のバレル２３の投入口に接続される主ホッパー３２と、予備ホッパー３１から主ホッパー３２にペレット１１を搬送する輸送部３３と、を有している。輸送部３３は、フィードスクリュー３４を回転可能に保持する筒体３５と、フィードスクリュー３４を回転駆動するモータ３６とを有している。モータ３６によってフィードスクリュー３４を回転駆動することによって、予備ホッパー３１から落下・供給されたペレット１１を搬送して、主ホッパー３２内へ供給する。フィーダー３０は、フィードスクリュー３４の回転速度を調整することによって、組成物１１の供給量を調整できる。
The feeder 30 includes a preliminary hopper 31 to which the pellets 11 are supplied by a loader (not shown), a main hopper 32 connected to the inlet of the barrel 23 of the extruder 20, and the pellets 11 from the preliminary hopper 31 to the main hopper 32. And a transport part 33 for transporting the The transport unit 33 includes a cylindrical body 35 that rotatably holds the feed screw 34 and a motor 36 that rotationally drives the feed screw 34. By rotating and driving the feed screw 34 by the motor 36, the pellet 11 dropped and supplied from the preliminary hopper 31 is conveyed and supplied into the main hopper 32. The feeder 30 can adjust the supply amount of the composition 11 by adjusting the rotation speed of the feed screw 34.
輸送部３３は、図示したスクリュー式のほか、コイル式、ベルト式、振動式、空気輸送、ピストン輸送、その他の方法を適用して、ペレット１１を搬送することができる。輸送部３３には、容量式定量フィーダー以外にも、重量式定量フィーダーも好適に用いることができる。主ホッパー３２には、減圧ユニットや、不活性ガスの導入ユニットを適宜設けることができる。
The transport unit 33 can transport the pellet 11 by applying a coil type, a belt type, a vibration type, pneumatic transportation, piston transportation, and other methods in addition to the illustrated screw type. In addition to the capacity-type quantitative feeder, a weight-type quantitative feeder can also be suitably used for the transport unit 33. The main hopper 32 can be appropriately provided with a decompression unit or an inert gas introduction unit.
バレル２３の周囲には、ペレット１１を溶融させる熱を加えるヒーター４１、４２、４３が設けられている。ヒーター４１、４２、４３は、スクリュー２１のフィードゾーンＣ１、移送ゾーンＣ２、およびメータリングゾーンＣ３のそれぞれに対応して設けられている。ヒーター４１、４２、４３は、例えば、温度制御が容易な電気ヒーターであるバンドヒーターを用いている。熱媒体を循環させるタイプのヒーターを用いることもできる。バレル２３の壁面温度を検出するため、熱電対などの温度センサー６１、６２、６３の先端部がバレル２３の壁面内に埋め込まれている。温度センサー６１、６２、６３の先端部をバレル２３の表面に密着させて取り付けることもできる。バンドヒーター４１、４２、４３への通電をオンオフ制御することによって、バレル２３の壁面温度を設定温度に維持する。設定温度は、組成物１１に含まれる材料の重合度、可塑剤の種類や添加量によって異なるが、例えば、１６０～１７０℃である。
Around the barrel 23, heaters 41, 42, and 43 for applying heat for melting the pellet 11 are provided. The heaters 41, 42, and 43 are provided corresponding to the feed zone C1, the transfer zone C2, and the metering zone C3 of the screw 21, respectively. As the heaters 41, 42, and 43, for example, band heaters that are electric heaters with easy temperature control are used. A type of heater that circulates the heat medium can also be used. In order to detect the wall surface temperature of the barrel 23, tip portions of temperature sensors 61, 62, 63 such as thermocouples are embedded in the wall surface of the barrel 23. The tips of the temperature sensors 61, 62, 63 can be attached in close contact with the surface of the barrel 23. By controlling the energization of the band heaters 41, 42, and 43 on and off, the wall surface temperature of the barrel 23 is maintained at the set temperature. The set temperature varies depending on the degree of polymerization of the material contained in the composition 11, the type of plasticizer and the amount added, but is, for example, 160 to 170 ° C.
ダイ５０は、押出機２０から押し出された溶融状態の組成物１１が通過する通路が形成されている。ダイ５０の先端部の開口形状は、医療用成形品１２の形状に合致した形状を有する。ダイ５０の基端部が、押出機２０の先端部に接続されている。
The die 50 has a passage through which the molten composition 11 extruded from the extruder 20 passes. The opening shape of the tip portion of the die 50 has a shape that matches the shape of the medical molded article 12. A proximal end portion of the die 50 is connected to a distal end portion of the extruder 20.
ダイ５０の基端部および先端部にも、押出機２０から押し出された溶融状態の組成物１１に熱を加えるダイ用ヒーター４４、４５が設けられている。バレル２３に設けたヒーター４１、４２、４３と同様に、ダイ用ヒーター４４、４５にもバンドヒーターを用いている。ダイ５０の壁面内に、ダイ５０の壁面温度を検出するため、熱電対などの温度センサー６４、６５の先端部が埋め込まれている。温度センサー６４、６５の先端部をダイ５０の表面に密着させて取り付けることもできる。バンドヒーター４４、４５への通電をオンオフ制御することによって、ダイ５０の壁面温度を設定温度に維持する。設定温度は、例えば、１６０～１７０℃である。
Die heaters 44 and 45 for applying heat to the molten composition 11 extruded from the extruder 20 are also provided at the proximal end and the distal end of the die 50. Similar to the heaters 41, 42, and 43 provided in the barrel 23, band heaters are also used for the die heaters 44 and 45. In order to detect the wall surface temperature of the die 50, tip portions of temperature sensors 64 and 65 such as thermocouples are embedded in the wall surface of the die 50. The tip portions of the temperature sensors 64 and 65 can be attached in close contact with the surface of the die 50. The wall surface temperature of the die 50 is maintained at a set temperature by performing on / off control of energization to the band heaters 44 and 45. The set temperature is, for example, 160 to 170 ° C.
押出成形装置１０は、さらに、押出機２０やフィーダー３０の作動を制御するコントローラー７０を有している。そして、フィーダー３０は、コントローラー７０によって作動が制御され、固形状に形成した組成物１１の供給量を、押出機２０内において組成物１１に剪断発熱を生じさせない量に調整される。押出機２０は、コントローラー７０によって作動が制御され、スクリュー２１の回転数が調整される。
The extrusion molding apparatus 10 further includes a controller 70 that controls the operation of the extruder 20 and the feeder 30. The operation of the feeder 30 is controlled by the controller 70, and the supply amount of the composition 11 formed in a solid state is adjusted to an amount that does not cause the composition 11 to generate shear heat in the extruder 20. The operation of the extruder 20 is controlled by the controller 70, and the number of rotations of the screw 21 is adjusted.
本実施形態にあっては、溝２２の深さｄが同じ深さに形成されたスクリュー２１を使用している。さらに、フィーダー３０は、フィードスクリュー３４の回転速度を調整することによって、固形状に形成した組成物１１を、押出機２０内において組成物１１に剪断発熱を生じさせない量に調整した供給量にて供給している。このため、押出機２０内において組成物１１が滞留することが抑えられ、さらに押出機２０内において組成物１１が過度に剪断発熱されることが抑えられる。したがって、成形品の焼けの原因となる２つの要因を抑制することができる。
In this embodiment, the screw 21 in which the depth d of the groove 22 is formed to the same depth is used. Further, the feeder 30 adjusts the rotation speed of the feed screw 34 to adjust the solid composition 11 to a quantity that does not cause shearing heat generation in the composition 11 in the extruder 20. Supply. For this reason, it is suppressed that the composition 11 stays in the extruder 20, and furthermore, it is suppressed that the composition 11 is excessively sheared and heated in the extruder 20. Therefore, it is possible to suppress two factors that cause burns of the molded product.
ここで、「押出機２０内において組成物１１に剪断発熱を生じさせない量」とは、スクリュー２１の溝２２の深さｄとの関係において組成物１１の供給量を定めることによって、「押出機２０内において組成物１１が滞留することを抑え、さらに押出機２０内において組成物１１が過度に剪断発熱されることを抑えることができる量」を意味している。したがって、組成物１１に剪断発熱が多少生じる量であっても、焼けの原因となる過度の剪断発熱が生じていない限りにおいて、その「組成物１１に剪断発熱が多少生じる量」は、「押出機２０内において組成物１１に剪断発熱を生じさせない量」に含まれると理解されなければならない。
Here, the “amount that does not cause shearing heat generation in the composition 11 in the extruder 20” means that the amount of the composition 11 supplied is determined in relation to the depth d of the groove 22 of the screw 21. This means an amount that can prevent the composition 11 from staying in the tube 20 and further prevent the composition 11 from excessively generating heat in the extruder 20. Therefore, even if the amount of shearing heat generated in the composition 11 is a certain amount, as long as excessive shearing heat generation that causes burning is not generated, the “amount of amount of shearing heat generation in the composition 11” is “extrusion”. It should be understood that it is included in the “amount that does not cause the composition 11 to generate a shear heating in the machine 20”.
押出機２０内において組成物１１が過度に剪断発熱されることを抑える観点から、押出機２０内における組成物１１の温度は「設定温度＋５℃以下」、より好ましくは「設定温度＋２℃以下」になるように、フィーダー３０によって組成物１１の供給量を制御することが好ましい。成形品の焼けの原因となる過度の剪断発熱を確実に抑制できるからである。尚、押出機２０内における組成物１１の温度は、温度センサー６１、６２、６３にて容易に確認できる。
From the viewpoint of suppressing the composition 11 from being excessively heated by shearing in the extruder 20, the temperature of the composition 11 in the extruder 20 is “set temperature + 5 ° C. or less”, more preferably “set temperature + 2 ° C. or less”. It is preferable to control the supply amount of the composition 11 by the feeder 30 so as to become. This is because it is possible to reliably suppress excessive shearing heat generation that causes burning of the molded product. The temperature of the composition 11 in the extruder 20 can be easily confirmed by the temperature sensors 61, 62, 63.
次に、作用を説明する。
Next, the operation will be described.
まず、ポリ塩化ビニル樹脂 １００質量部に対して、エステル可塑剤 ３０～１６０質量部、エポキシ可塑剤 ５～２５質量部、および亜鉛石鹸およびカルシウム石鹸 ０．０１～０．１質量部（合計量）を含む組成物１１を、固形状のペレット１１に形成する。
First, with respect to 100 parts by mass of polyvinyl chloride resin, 30 to 160 parts by mass of ester plasticizer, 5 to 25 parts by mass of epoxy plasticizer, and 0.01 to 0.1 parts by mass of zinc soap and calcium soap (total amount) The composition 11 containing is formed into a solid pellet 11.
ヒーター４１、４２、４３およびダイ用ヒーター４４、４５への通電をオンオフ制御することによって、バレル２３の壁面温度およびダイ５０の壁面温度を設定温度に昇温する。
The wall surface temperature of the barrel 23 and the wall surface temperature of the die 50 are raised to the set temperature by on / off control of energization to the heaters 41, 42, 43 and the die heaters 44, 45.
フィーダー３０は、溝２２の深さｄが同じ深さに形成された押出機２０のスクリュー２１に、ペレット１１を供給する。このとき、フィーダー３０は、フィードスクリュー３４の回転速度を調整することによって、ペレット１１を、押出機２０内において組成物１１に剪断発熱を生じさせない量に調整した供給量にて供給する。
The feeder 30 supplies the pellet 11 to the screw 21 of the extruder 20 in which the depth d of the groove 22 is formed to the same depth. At this time, the feeder 30 supplies the pellets 11 by adjusting the rotation speed of the feed screw 34 so that the pellets 11 are adjusted to an amount that does not cause shearing heat generation in the composition 11 in the extruder 20.
スクリュー２１に供給されたペレット１１は、ヒーター４１、４２、４３からの熱が加えられて溶融する。溶融した組成物１１は、スクリュー２１の溝２２を通ってスクリュー２１の先端まで達すると、溝２２による誘導がなくなるため、前進する力が弱くなる。溶融状態の組成物１１の前進が抑制されるので、メータリングゾーンＣ３では溶融状態の組成物１１の圧力は若干高くなる。ただし、この圧力の増加は、組成物１１に剪断発熱を生じさせるものではない。
The pellet 11 supplied to the screw 21 is melted by applying heat from the heaters 41, 42, 43. When the melted composition 11 reaches the tip of the screw 21 through the groove 22 of the screw 21, since the induction by the groove 22 is lost, the forward force is weakened. Since the advance of the molten composition 11 is suppressed, the pressure of the molten composition 11 is slightly increased in the metering zone C3. However, this increase in pressure does not cause the composition 11 to generate shear heat.
そして、押出機２０から押し出された溶融状態の組成物１１をダイ５０によって医療用成形品１２の形状に成形する。押出成形中は、ヒーター４１、４２、４３およびダイ用ヒーター４４、４５への通電をオンオフ制御することによって、バレル２３の壁面温度およびダイ５０の壁面温度を設定温度に維持する。
Then, the molten composition 11 extruded from the extruder 20 is molded into the shape of the medical molded article 12 by the die 50. During extrusion molding, the wall surface temperature of the barrel 23 and the wall surface temperature of the die 50 are maintained at the set temperature by on / off control of energization to the heaters 41, 42, 43 and the die heaters 44, 45.
以上説明したように、本実施形態の医療用成形品の押出成形技術によれば、溝２２の深さｄが同じ深さに形成されたスクリュー２１を使用し、さらに、固形状に形成した組成物１１を、押出機２０内において組成物１１に剪断発熱を生じさせない量に調整した供給量にて供給している。このため、押出機２０内において組成物１１が滞留することが抑えられ、さらに押出機２０内において組成物１１が過度に剪断発熱されることが抑えられる。成形品の焼けの原因となる２つの要因を抑制できる結果、少ない量の金属石鹸であっても着色度の低い（白色度が高くかつ黄色度が低い）医療用成形品１２を低コストに製造できる。
As described above, according to the extrusion molding technique for a medical molded product of the present embodiment, the screw 21 formed with the same depth d of the groove 22 is used, and the composition formed into a solid form is further used. The product 11 is supplied in the extruder 20 at a supply amount adjusted to an amount that does not cause shearing heat generation in the composition 11. For this reason, it is suppressed that the composition 11 stays in the extruder 20, and furthermore, it is suppressed that the composition 11 is excessively sheared and heated in the extruder 20. As a result of suppressing two factors that cause burns of molded products, low-colored (high whiteness and low yellowness) medical molded products 12 are manufactured at low cost even with a small amount of metal soap. it can.
押出機２０内における組成物１１の温度は、「設定温度＋５℃以下」になるようにしている。このように構成することによって、成形品の焼けの原因となる過度の剪断発熱を確実に抑制して、少ない量の金属石鹸であっても着色度の低い（白色度が高くかつ黄色度が低い）医療用成形品１２を低コストに製造できる。
The temperature of the composition 11 in the extruder 20 is set to “set temperature + 5 ° C. or less”. By constituting in this way, excessive shearing heat generation that causes burning of the molded product is surely suppressed, and even with a small amount of metal soap, the degree of coloring is low (high whiteness and low yellowness). ) The medical molded article 12 can be manufactured at a low cost.
医療用成形品１２としてのチューブを成形する押出成形装置１０について説明したが、本発明はこの場合に限定されるものではない。輸液、輸血用のバッグ、これらのバッグに連結されるチューブなど、様々な用途の医療用成形品を成形するために、押出成形装置１０を適宜改変して適用することができる。
Although the extrusion apparatus 10 for forming a tube as the medical molded article 12 has been described, the present invention is not limited to this case. In order to form medical molded products for various uses such as infusion solutions, blood transfusion bags, and tubes connected to these bags, the extrusion molding apparatus 10 can be appropriately modified and applied.
本発明の効果を、以下の実施例および比較例を用いて説明する。ただし、本発明の技術的範囲が以下の実施例のみに制限されるわけではない。なお、下記実施例において、特記しない限り、操作は室温（２５℃）で行われた。また、特記しない限り、「％」および「部」は、それぞれ、「質量％」および「質量部」を意味する。
The effect of the present invention will be described using the following examples and comparative examples. However, the technical scope of the present invention is not limited only to the following examples. In the following examples, the operation was performed at room temperature (25 ° C.) unless otherwise specified. Unless otherwise specified, “%” and “part” mean “% by mass” and “part by mass”, respectively.
実施例１
ポリ塩化ビニル樹脂（株式会社カネカ製、ＫＳ－１７００、平均重合度：１７００） １００ｋｇ、エステル可塑剤としてフタル酸ビス（２－エチルヘキシル）（ＤＥＨＰ） ５２ｋｇ、エポキシ可塑剤としてエポキシ化大豆油（株式会社ＡＤＥＫＡ製、Ｏ－１３０Ｐ） ８ｋｇ、安定剤としてＣａ－Ｚｎ系安定剤（株式会社ＡＤＥＫＡ製、商品名：アデカスタブ３７、ステアリン酸カルシウム含量：約７．５７質量％、ステアリン酸亜鉛含有量：約１０．１質量％） ０．０７ｋｇ、およびシリコーンオイル（信越化学 商品名：ＫＦ－５０） ０．１５ｋｇを混合し、ポリ塩化ビニル樹脂組成物を調製した。なお、このポリ塩化ビニル樹脂組成物中、ステアリン酸カルシウム及びステアリン酸亜鉛は、それぞれ、０．００５３ｋｇ及び０．００７０７ｋｇ含まれている。 Example 1
Polyvinyl chloride resin (manufactured by Kaneka Corporation, KS-1700, average polymerization degree: 1700) 100 kg, ester plasticizer bis (2-ethylhexyl) phthalate (DEHP) 52 kg, epoxy plasticizer epoxidized soybean oil (Co., Ltd.) ADEKA, O-130P) 8 kg, Ca—Zn stabilizer as a stabilizer (manufactured by ADEKA, trade name: ADK STAB 37, calcium stearate content: about 7.57% by mass, zinc stearate content: about 10. (1% by mass) 0.07 kg and 0.15 kg of silicone oil (Shin-Etsu Chemical brand name: KF-50) were mixed to prepare a polyvinyl chloride resin composition. In this polyvinyl chloride resin composition, 0.0053 kg and 0.00707 kg of calcium stearate and zinc stearate are contained, respectively.
ポリ塩化ビニル樹脂（株式会社カネカ製、ＫＳ－１７００、平均重合度：１７００） １００ｋｇ、エステル可塑剤としてフタル酸ビス（２－エチルヘキシル）（ＤＥＨＰ） ５２ｋｇ、エポキシ可塑剤としてエポキシ化大豆油（株式会社ＡＤＥＫＡ製、Ｏ－１３０Ｐ） ８ｋｇ、安定剤としてＣａ－Ｚｎ系安定剤（株式会社ＡＤＥＫＡ製、商品名：アデカスタブ３７、ステアリン酸カルシウム含量：約７．５７質量％、ステアリン酸亜鉛含有量：約１０．１質量％） ０．０７ｋｇ、およびシリコーンオイル（信越化学 商品名：ＫＦ－５０） ０．１５ｋｇを混合し、ポリ塩化ビニル樹脂組成物を調製した。なお、このポリ塩化ビニル樹脂組成物中、ステアリン酸カルシウム及びステアリン酸亜鉛は、それぞれ、０．００５３ｋｇ及び０．００７０７ｋｇ含まれている。 Example 1
Polyvinyl chloride resin (manufactured by Kaneka Corporation, KS-1700, average polymerization degree: 1700) 100 kg, ester plasticizer bis (2-ethylhexyl) phthalate (DEHP) 52 kg, epoxy plasticizer epoxidized soybean oil (Co., Ltd.) ADEKA, O-130P) 8 kg, Ca—Zn stabilizer as a stabilizer (manufactured by ADEKA, trade name: ADK STAB 37, calcium stearate content: about 7.57% by mass, zinc stearate content: about 10. (1% by mass) 0.07 kg and 0.15 kg of silicone oil (Shin-Etsu Chemical brand name: KF-50) were mixed to prepare a polyvinyl chloride resin composition. In this polyvinyl chloride resin composition, 0.0053 kg and 0.00707 kg of calcium stearate and zinc stearate are contained, respectively.
次に、このポリ塩化ビニル樹脂組成物を、ペレットに形成し、上述した医療用成形品の押出成形装置を使用して、内径がφ３．０ｍｍ、外径がφ４．４ｍｍであるチューブを押出成形した。使用したペレットはφ３～４ｍｍの球形形状を有し、供給量を４ｋｇ／ｈｒに設定した。押出機のバレルの内径はφ２２ｍｍである。スクリューの回転速度を５０ｒｐｍに設定した。押出成形装置において、溝の深さが同じ深さに形成された押出機のスクリューに、ペレットを、押出機内において組成物に剪断発熱を生じさせない量に調整した供給量にて供給した。そして、スクリューに供給されたペレットにヒーターからの熱を加えて溶融し、押出機から押し出された溶融状態の組成物をダイによってチューブの形状に成形した。ヒーターの設定温度は、ヒーター４１については１６０℃、ヒーター４２～４５については１７０℃とした。
Next, this polyvinyl chloride resin composition is formed into pellets, and a tube having an inner diameter of φ3.0 mm and an outer diameter of φ4.4 mm is extrusion-molded using the above-described medical molding product extrusion molding apparatus. did. The pellets used had a spherical shape with a diameter of 3-4 mm, and the supply rate was set to 4 kg / hr. The inner diameter of the barrel of the extruder is 22 mm. The rotational speed of the screw was set to 50 rpm. In the extrusion molding apparatus, pellets were supplied to an extruder screw formed to have the same groove depth at a supply amount adjusted so as not to cause shearing heat generation in the composition in the extruder. Then, the pellets supplied to the screw were melted by applying heat from a heater, and the molten composition extruded from the extruder was formed into a tube shape by a die. The set temperature of the heater was 160 ° C. for the heater 41 and 170 ° C. for the heaters 42 to 45.
得られたチューブについて白色度及び黄色度を測定したところ、それぞれ、２５．８及び２．５であった。この結果から、本実施例のチューブは、少ない安定剤量（亜鉛石鹸およびカルシウム石鹸）であっても、高い白色度及び低い黄色度を示すことが分かる。
When the whiteness and yellowness of the obtained tube were measured, they were 25.8 and 2.5, respectively. From this result, it can be seen that the tube of this example shows high whiteness and low yellowness even with a small amount of stabilizer (zinc soap and calcium soap).
実施例２
実施例１において、Ｃａ－Ｚｎ系安定剤（株式会社ＡＤＥＫＡ製、商品名：アデカスタブ３７）の配合量を０．２１ｋｇに変更した以外は、実施例１と同様にしてチューブを製造した。 Example 2
A tube was produced in the same manner as in Example 1 except that the amount of Ca—Zn stabilizer (trade name: ADK STAB 37 manufactured by ADEKA Corporation) was changed to 0.21 kg.
実施例１において、Ｃａ－Ｚｎ系安定剤（株式会社ＡＤＥＫＡ製、商品名：アデカスタブ３７）の配合量を０．２１ｋｇに変更した以外は、実施例１と同様にしてチューブを製造した。 Example 2
A tube was produced in the same manner as in Example 1 except that the amount of Ca—Zn stabilizer (trade name: ADK STAB 37 manufactured by ADEKA Corporation) was changed to 0.21 kg.
得られたチューブについて白色度及び黄色度を測定したところ、それぞれ、２８．４及び１．１であった。この結果から、本実施例のチューブは、少ない安定剤量（亜鉛石鹸およびカルシウム石鹸）であっても、高い白色度及び低い黄色度を示すことが分かる。
When the whiteness and yellowness of the obtained tube were measured, they were 28.4 and 1.1, respectively. From this result, it can be seen that the tube of this example shows high whiteness and low yellowness even with a small amount of stabilizer (zinc soap and calcium soap).
実施例３
実施例１において、Ｃａ－Ｚｎ系安定剤（株式会社ＡＤＥＫＡ製、商品名：アデカスタブ３７）の配合量を０．３５ｋｇに変更した以外は、実施例１と同様にしてチューブを製造した。 Example 3
A tube was produced in the same manner as in Example 1 except that the compounding amount of the Ca—Zn stabilizer (manufactured by ADEKA Corporation, trade name: ADK STAB 37) was changed to 0.35 kg.
実施例１において、Ｃａ－Ｚｎ系安定剤（株式会社ＡＤＥＫＡ製、商品名：アデカスタブ３７）の配合量を０．３５ｋｇに変更した以外は、実施例１と同様にしてチューブを製造した。 Example 3
A tube was produced in the same manner as in Example 1 except that the compounding amount of the Ca—Zn stabilizer (manufactured by ADEKA Corporation, trade name: ADK STAB 37) was changed to 0.35 kg.
得られたチューブについて白色度及び黄色度を測定したところ、それぞれ、２８．０及び１．２であった。この結果から、本実施例のチューブは、少ない安定剤量（亜鉛石鹸およびカルシウム石鹸）であっても、高い白色度及び低い黄色度を示すことが分かる。
When the whiteness and yellowness of the obtained tube were measured, they were 28.0 and 1.2, respectively. From this result, it can be seen that the tube of this example shows high whiteness and low yellowness even with a small amount of stabilizer (zinc soap and calcium soap).
実施例４
実施例１において、Ｃａ－Ｚｎ系安定剤（株式会社ＡＤＥＫＡ製、商品名：アデカスタブ３７）の配合量を０．７０ｋｇに変更した以外は、実施例１と同様にしてチューブを製造した。 Example 4
A tube was produced in the same manner as in Example 1, except that the amount of Ca—Zn stabilizer (trade name: ADK STAB 37 manufactured by ADEKA Corporation) was changed to 0.70 kg.
実施例１において、Ｃａ－Ｚｎ系安定剤（株式会社ＡＤＥＫＡ製、商品名：アデカスタブ３７）の配合量を０．７０ｋｇに変更した以外は、実施例１と同様にしてチューブを製造した。 Example 4
A tube was produced in the same manner as in Example 1, except that the amount of Ca—Zn stabilizer (trade name: ADK STAB 37 manufactured by ADEKA Corporation) was changed to 0.70 kg.
得られたチューブについて白色度及び黄色度を測定したところ、それぞれ、２７．６及び０．８であった。この結果から、本実施例のチューブは、少ない安定剤量（亜鉛石鹸およびカルシウム石鹸）であっても、高い白色度及び低い黄色度を示すことが分かる。
When the whiteness and yellowness of the obtained tube were measured, they were 27.6 and 0.8, respectively. From this result, it can be seen that the tube of this example shows high whiteness and low yellowness even with a small amount of stabilizer (zinc soap and calcium soap).
本出願は、２０１５年３月２６日に出願された日本特許出願番号２０１５－０６４４４９号に基づいており、その開示内容は、参照され、全体として、組み入れられている。
This application is based on Japanese Patent Application No. 2015-064449 filed on March 26, 2015, the disclosure of which is referenced and incorporated as a whole.
１０ 医療用成形品の押出成形装置、
１１ ペレット（組成物）、
１２ チューブ（医療用成形品）、
２０ 押出機、
２１ スクリュー、
２２ 溝、
２３ バレル、
３０ フィーダー、
３４ フィードスクリュー、
４１、４２、４３ ヒーター、
４４、４５ ダイ用ヒーター、
５０ ダイ、
６１、６２、６３ 温度センサー、
６４、６５ 温度センサー、
７０ コントローラー、
Ｃ１ フィードゾーン、
Ｃ２ 移送ゾーン、
Ｃ３ メータリングゾーン、
ｄ 溝の深さ。 10 Extrusion molding equipment for medical molded products,
11 pellets (composition),
12 Tube (medical product),
20 extruder,
21 screws,
22 grooves,
23 barrels,
30 Feeder,
34 Feed screw,
41, 42, 43 heater,
44, 45 Die heater,
50 dies,
61, 62, 63 Temperature sensor,
64, 65 temperature sensor,
70 controller,
C1 feed zone,
C2 transfer zone,
C3 metering zone,
d Groove depth.
１１ ペレット（組成物）、
１２ チューブ（医療用成形品）、
２０ 押出機、
２１ スクリュー、
２２ 溝、
２３ バレル、
３０ フィーダー、
３４ フィードスクリュー、
４１、４２、４３ ヒーター、
４４、４５ ダイ用ヒーター、
５０ ダイ、
６１、６２、６３ 温度センサー、
６４、６５ 温度センサー、
７０ コントローラー、
Ｃ１ フィードゾーン、
Ｃ２ 移送ゾーン、
Ｃ３ メータリングゾーン、
ｄ 溝の深さ。 10 Extrusion molding equipment for medical molded products,
11 pellets (composition),
12 Tube (medical product),
20 extruder,
21 screws,
22 grooves,
23 barrels,
30 Feeder,
34 Feed screw,
41, 42, 43 heater,
44, 45 Die heater,
50 dies,
61, 62, 63 Temperature sensor,
64, 65 temperature sensor,
70 controller,
C1 feed zone,
C2 transfer zone,
C3 metering zone,
d Groove depth.
Claims (8)
- ポリ塩化ビニル樹脂 １００質量部に対して、
エステル可塑剤 ３０～１６０質量部、
エポキシ可塑剤 ５～２５質量部、および
亜鉛石鹸およびカルシウム石鹸 ０．０１～０．１質量部（合計量）
と含む組成物を押出成形されてなり、
白色度（Ｗ．Ｉ．）が２５以上でかつ黄色度（Ｙ．Ｉ．）が３．５以下である、医療用成形品。 For 100 parts by mass of polyvinyl chloride resin,
30 to 160 parts by mass of ester plasticizer,
Epoxy plasticizer 5 to 25 parts by mass, and zinc soap and calcium soap 0.01 to 0.1 parts by mass (total amount)
Extruded composition containing
A medical molded article having a whiteness (WI) of 25 or more and a yellowness (YI) of 3.5 or less. - 請求項１に記載の組成物を押出成形し、白色度（Ｗ．Ｉ．）が２５以上でかつ黄色度（Ｙ．Ｉ．）が３．５以下である医療用成形品を成形する、医療用成形品の押出成形方法であって、
溝の深さが同じ深さに形成された押出機のスクリューに、固形状に形成した前記組成物を、前記押出機内において前記組成物に剪断発熱を生じさせない量に調整した供給量にて供給し、
前記スクリューに供給された固形状の前記組成物にヒーターからの熱を加えて溶融し、
前記押出機から押し出された溶融状態の前記組成物をダイによって医療用成形品の形状に成形する、医療用成形品の押出成形方法。 The composition according to claim 1 is extruded to form a medical molded article having a whiteness (WI) of 25 or more and a yellowness (YI) of 3.5 or less. A method for extrusion molding of molded products,
Supplying the composition formed in a solid form to the screw of an extruder formed with the same groove depth at a supply amount adjusted so as not to cause shearing heat generation in the composition in the extruder. And
The solid composition supplied to the screw is melted by applying heat from a heater,
A method for extruding a medical molded product, wherein the composition in a molten state extruded from the extruder is molded into a shape of a medical molded product by a die. - 前記押出機内において前記組成物の温度が「設定温度＋５℃」以下である、請求項２に記載の医療用成形品の押出成形方法。 The method for extruding a medical molded article according to claim 2, wherein the temperature of the composition in the extruder is "set temperature + 5 ° C" or less.
- 前記医療用成形品が、輸液用のバッグ、輸血用のバッグ、またはチューブである、請求項２または請求項３に記載の医療用成形品の押出成形方法。 The method for extruding a medical molded product according to claim 2 or 3, wherein the medical molded product is a bag for infusion, a bag for blood transfusion, or a tube.
- 請求項１に記載の組成物を押出成形し、白色度（Ｗ．Ｉ．）が２５以上でかつ黄色度（Ｙ．Ｉ．）が３．５以下である医療用成形品を成形する、医療用成形品の押出成形装置であって、
溝の深さが同じ深さに形成されたスクリューをバレル内に回転駆動自在に配置した押出機と、
固形状に形成した前記組成物を前記スクリューに供給するとともに前記組成物の供給量を調整自在なフィーダーと、
前記スクリューに供給された固形状の前記組成物を溶融させる熱を加えるヒーターと、
前記押出機から押し出された溶融状態の前記組成物を医療用成形品の形状に成形するダイと、を有し、
前記フィーダーは、前記組成物の供給量を、前記押出機内において前記組成物に剪断発熱を生じさせない量に調整する、医療用成形品の押出成形装置。 The composition according to claim 1 is extruded to form a medical molded article having a whiteness (WI) of 25 or more and a yellowness (YI) of 3.5 or less. An extrusion molding apparatus for a molded product,
An extruder in which a screw formed with the same groove depth is rotatably arranged in a barrel;
A feeder capable of adjusting the supply amount of the composition while supplying the composition formed in a solid state to the screw;
A heater for applying heat for melting the solid composition supplied to the screw;
A die that molds the composition in a molten state extruded from the extruder into the shape of a medical molded article,
The feeder is an apparatus for extruding a medical molded article that adjusts the supply amount of the composition to an amount that does not cause shearing heat generation in the composition in the extruder. - 前記押出機内において前記組成物の温度が「設定温度＋５℃」以下である、請求項５に記載の医療用成形品の押出成形装置。 The medical molding product extrusion molding apparatus according to claim 5, wherein the temperature of the composition in the extruder is "set temperature + 5 ° C" or lower.
- 前記押出機から押し出された溶融状態の前記組成物に熱を加えるダイ用ヒーターをさらに有する、請求項５または請求項６に記載の医療用成形品の押出成形装置。 The apparatus for extruding a medical molded article according to claim 5 or 6, further comprising a die heater for applying heat to the molten composition extruded from the extruder.
- 前記医療用成形品が、輸液用のバッグ、輸血用のバッグ、またはチューブである、請求項５～請求項７のいずれか１項に記載の医療用成形品の押出成形装置。 The medical molded product extrusion molding apparatus according to any one of claims 5 to 7, wherein the medical molded product is a bag for infusion, a bag for blood transfusion, or a tube.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201680018228.0A CN107428957B (en) | 2015-03-26 | 2016-03-04 | Medical molded article, extrusion molding method for medical molded article, and extrusion molding device for medical molded article |
| JP2017508167A JP6788575B2 (en) | 2015-03-26 | 2016-03-04 | Medical molded products, extrusion molding methods for medical molded products, and extrusion molding equipment for medical molded products |
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| JP2015-064449 | 2015-03-26 | ||
| JP2015064449 | 2015-03-26 |
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| WO2016152466A1 true WO2016152466A1 (en) | 2016-09-29 |
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| PCT/JP2016/056880 WO2016152466A1 (en) | 2015-03-26 | 2016-03-04 | Molded article for medical use, extrusion molding method for molded article for medical use, and extrusion molding device for molded article for medical use |
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| JP (1) | JP6788575B2 (en) |
| CN (1) | CN107428957B (en) |
| WO (1) | WO2016152466A1 (en) |
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| CN112759858B (en) * | 2020-12-24 | 2022-12-06 | 金发科技股份有限公司 | Injection molding grade modified PVC material and preparation method and application thereof |
| TWI762383B (en) * | 2021-07-14 | 2022-04-21 | 臺灣塑膠工業股份有限公司 | Anti-biofouling material, human body tissue-contacting medical tube containing the same and manufacturing method of the same |
| CN113881161B (en) * | 2021-10-20 | 2022-09-23 | 台湾塑胶工业股份有限公司 | Anti-sticking material, medical catheter contacting human tissue containing same and manufacturing method thereof |
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| JPS60137644A (en) * | 1983-12-26 | 1985-07-22 | 住友ベークライト株式会社 | Composite molded material of soft vinyl chloride group resincomposition and addition polymerization type silicone rubber |
| JPS6133661A (en) * | 1984-02-02 | 1986-02-17 | テルモ株式会社 | Medical instrument |
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Also Published As
| Publication number | Publication date |
|---|---|
| JP6788575B2 (en) | 2020-11-25 |
| CN107428957A (en) | 2017-12-01 |
| CN107428957B (en) | 2023-09-22 |
| JPWO2016152466A1 (en) | 2018-01-18 |
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